Inorganic Chemistry Douglas Pdf Free Download

Discover the world's research

• 20+ million members
• 135+ million publications
• 700k+ research projects

Join for free

INORGANIC

CHEMISTRY

1.

INTRODUCTION

By

E.

A.

V.

Ebsworth

(

University Chemical

Laboratory,

Cambridge)

J.

Lewis

(The

'victoria University

of

Manchester)

THE

general form of the

Annual Reports

is

essentially the same as last year,

except for the addition

of

a section on kinetics

of

inorganic reactions. Per-

haps the most important development

in

the field of inorganic chemistry

has been the isolation of complexes of nitrogen with ruthenium and

iridium, and the conversion

of

nitrogen into ammonia by transition-metal

complexes.s This

will

obviously provide an impetus

for

considerable effort

in this field

of

chemistry over the next few years.

As

noted last year, the rate of publication

of

Papers continues to

in-

crease, and hence the coverage

of

the literature

in

a report

of

this type

becomes more subjective.

A

number

of

review journals have appeared

to

help in the assimilation of

this

large flow

of

Papers, and it is

to

be hoped that

these reviews will involve the comprehensive as well as the more general

review articles. Among the new series which appeared this

year

are

Tramition

Metal

Chmistry,

vol.

1--III,4

Structure

and

Bonding,S

Organo-

metallic Chemistry Reviews,6

and

Co-ordination Chemistry Reviews.7

An

additional communication journal,

Inorganic and Nuclear Chemistry Letters,8

the first number

of

which is dated October

1965,

and the second volume

of

Phillips and Williams's

book

on

''

Inorganic Chemistry

"

have also been

published.

A.

D.

Allen and

C.

V.

Senoff,

Chem. Comm.,

1966, 621.

a

J.

P. Collman

and

J.

W.

Kang,

J.

Amer. Chern.

Xoc.,

1966,88,

3459.

M.

E.

Vol'pin and

V.

B.

Shur,

Nature,

1966,

209,

1236.

Transition Metal Chemistry,

ed.

R.

L.

Carlin,

Arnold, London,

1966.

Structure

and

Bonding,

Springer, New York,

1966.

(I

Organmetallic Chemistry Reviews,

Elsevier, Amsterdam.

Coordination Chemistry Reviews,

ed.

A.

B.

P.

Lever, Elsevier, Amsterdam.

a

Inorganic and Nuclear Chemistry Letters,

Pergamon Press, New

York.

O

C.

S.

G.

Phillips and

R.

J.

P.

Williams,

"

Inorganic Chemistry,"

vol.

11,

Clarendon

Press, Oxford,

1966.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

/ Table of Contents for this issue

2.

KINETICS AND MECHANISMS

OF

INORGANIC REACTIONS

By

J.

Burgess

(Chemistry Department, Leicester University)

As

is usual in these Reports

it

is only possible to mention

a

proportion,

here about a quarter, of the year's relevant references.

In

the process

of

selection

all

references to two active fields which overlap organic chemistry,

organo-silicon and -germanium chemistry, and oxidations

of

organic com-

pounds by inorganic species, have been eliminated. The emphasis on

reactions of transition-metal complexes in this Report reflects the continued

major interest in this aspect

of

inorganic kinetics. [Throughout this Report

L

stands for any ligand, as specified in the text,

X

stands for

a

halogen atom

((31, Br,

I)

unless otherwise stated, and

AH$

and

A$

represent enthalpies

and entropies of activation. References to the Russian literature quote

page numbers

of

the English translations.]

Redox

Reactions.-There has again been much

work

on inner-sphere

reductions

of

cobalt(m) Complexes by chromium(@. cis-[Co(en),(N,),]+ and

cis-[Co(NHC,),(N,),]+ react by parallel paths involving a single or a double

azide bridge.l For [Co(en>,(NCS)Xln+

(X

=

C1, NCS,

NH,,

OH,)

chrom-

ium@) attack can occur at either nitrogen

or

sulphur to form the thiocyanate

bridge., The importance

of

steric factors and ligand reducibility have been

investigated for reduction

of

thirty

carboxylatopenta-amminecobalt(m)

complexes

;

for aromatic carboxylate ligands containing anitro group there

is evidence for chromium(n) attack at the nitro group.3 The rate of ring

closure of [Cr(

OH2),(

O,C*CH,*CO,H)]

,+,

containing unidentate malonate, to

the chelate

[Cr(

OH2),(

O,C*CH,*CO,)]

+

is

much slower than the rate of reduc-

tion

of

[Co(NH,),(

02C*CH2*C02H)]2+

by chromium(n)

.4

This evidence,

together with rate constants and product distribution from analogous reduc-

tions of malonate half-ester c~mplexes,~ refutes the earlier postulate of

chromium(@ attack at the remote oxygen atom

of

the malonate ligand.

The

transition state now suggested contains chromium bonded to oxygen

atoms from both carboxyl groups of the bridging malonate. The nature

of

intermediates in the chromium(

11)

reduction

of

nicotinamido- and isonicotin-

amido-penta-amminecobalt(m)

casts

further doubt on the general applica-

bility of the remote attack hypothesis.6 Reaction rates

of

chromium(I1) with

cis-

and truns-[Co(en),(OH2),]3+ and [Co(en),(OH2)(NH,)33f indicate a

trans

effect, though this is much less marked than for reduction by iron(=).'

Electron exchange in the chromium(lr)-[Cr( OH2),(NH,)I3+ reaction

occurs by an inner-sphere mechanism.8 The detection

of

transient iron(m)

*

A.

Haim,

J.

Amer. Chem.

SOC.,

1966,

88,

2324.

a

A.

Haim and

N.

Sutin,

J.

Arner.

Chem.

Soc.,

1966, 88,434.

E.

S.

Gould,

J.

Amer. Chem.

SOC.,

1966,

88,

2983.

D.

€I.

Huchital and

H.

Taube,

Inorg.

Chem.,

1965,

4,

1660.

D.

H.

Huchital

and

H.

Taube,

J.

Amer.

Chem.

Soc.,

1965,

87,

5371.

6

F.

R.

Nordmeyer

and

H.

Taube,

J.

Amer. Chem.

SOC.,

1966,

88,

4295.

7

R.

D.

Cannon

and

J.

E.

Earley,

J.

Amer.

Chem.Soc.,

1965,87,5264; 1966,88,1872.

*

J.

H.

Espenson

and

D.

W.

Carlyle,

Inorg.

Chem.,

1966, 5,586.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

BURGESS

:

KINETICS

OF

INORGANIC

REACTIONS

131

complexes by fast reaction techniques

in

the reaction of iron(=) with several

cobalt@) complexes confirms that these are also inner-sphere

reaction^.^

Transition-state

chromium-oxygen-vanadium

bridging has now been demon-

stratedl0 and may be compared

with

earlier reports of Cr-O-Cr and

V-0-V

bridging.

V-0-U

bridging occurs

in

the vanadium(m)-uranium(vr) re-

action.ll

The use of the "oxygen isotopic fractionation factor,"

f,

the ratio of

rates,

d

In

lS0/d

In

l*O, has been discussed as a means

for

differentiating

between inner-sphere and outer-sphere oxidations. For inner-sphere

oxida-

tions,

e.g.

[Co(NH3),(

OH)]2+-chromium(rr), where

Co-0

bond stretching

is

important

in

the formation of the transition state,

f

is significantly larger

than for outer-sphere oxidations,

e.g.

[CO(NH~),(OH)]~+-[RU(~H,),]~+.

Vanadium(r1) and europium(rr) reductions have

f

values similar to those

for

[Ru(NH,),]~+

reductions, suggesting that these cations, unlike chromium(n),

reduce penta-amminecobalt(m) complexes by an outer-sphere mechanism.12

However, there

is

evidence for chlorine bridging in the europium(rr)-

chromium

(m)

system.

l3

There have been several studies

of

outer-sphere redox reactions. Rates

and activation parameters have been determined by the temperature- jump

technique for the

hexachloroiridate(n)-hexabromoiridate(m)

forward and

reverse reactions.l4 Electron transfer rates in the manganate-perruthenate

system have been reported

;

in the ruthenate-perruthenate system rates

were too fast to follow. These results were compared with rnanganate-

permanganate electron exchange data in the light

of

Marcus's theories.15

l[ron(m) oxidation of [Ta6CIl,]

2+

to [Ta,C1,2]4+ proceeds by two one-electron

transfers.16 Electron transfer

in

the system iron(=)-iron(m) in complexes

with 1,lO-phenanthroline (unsubstituted and methyl derivatives) is too fast

to measure even from n.m.r. line-broadening.l7 Rates of oxidation of

ruthenium@) complexes of substituted

1

,lo-phenanthrolines by cerium(rv)

are consistent with Marcus's equations for outer-sphere oxidations.l*

Activation energies and frequency factors

for

oxidation of the same com-

plexes by thallium(~n),~~ and of

iron(@

Complexes

of

the same ligands

by

peroxodisulphate,

*O

show linear correlation

over

a

wide range

of

values.

The question

of

one-

or

two-electron transfers

in

redox reactions involving

thallium has been discussed in several other papers.

In

the silver(n-

thallium(1) reaction

in

nitric acid, two one-electron steps

are

indicated

;21

similarly, results of vanadium( m)-thallium(

III)

experiments rule out simul-

A.

Haim

and

N.

Sutin,

J.

Amer.

Chem.

SOC.,

1966,

88,

5343.

T.

W.

Newton and

F.

B.

Baker,

J.

Phys.

C'hem.,

1966,

70,

1943.

lo

J.

H.

Espenson,

Inorg.

Chem.,

1965,

4,

1533.

l3

H.

Diebler,

I?.

H.

Dodel,

and

H.

Taube,

Inorg.

Clzern.,

1966,

5,

1685.

l3

A.

Adin and

A.

G.

Sykcs,

J.

Chem.

SOC.

(A),

1966,

1230.

l5

E.

V.

Luoma and

C.

H.

Brubacker,

Inorg.

Chena.,

1966,

5,

1618, 1637.

l6

J.

H.

Espenson and

R.

E.

McCarley,

J.

Amer. Chern.

Xoc.,

1966,

88,

1053.

l7

D.

W.

Larsen and

A.

C.

Wahl,

J.

Chem.

Phys.,

1965,

43,

3765.

l8

J.

D. Miller and

R.

H.

Prince,

J.

Chem.

SOC.

(A),

1966,

1370.

J.

D.

Miller and

R.

H.

Prince,

J.

Chem.

SOC.

(A),

1966,

1048.

8o

J.

Burgess and

R.

H.

Frince,

J.

Chem.

SOC.

(A),

1966, 1772.

21

R.

'VV.

Dundon and

J.

W.

Gryder,

Inorg.

Chern.,

1863,

5,986.

P.

Hurwitz and

K.

Kustin,

Trans.

Paraday

SOC.,

1966,

62,

427.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

132

INORGANIC CHEMISTRY

taneous two-electron transfer.22 However, kinetics of the vanadium(@-

tUurn(m) reaction, and relative rates of reaction

of

vanadium(rr)

and

vanadium(rn) with thallium(m), suggest two-electron transfer in

this

case.23

The importance

of

ion-pairing

in

redox reactions has been illustrated for

reaction of ferrocyanide with peroxodisulphate, where variation

of

rate with

potassium ion concentration indicates that [KFe(

CN),]3-

and

[KS,O,]-

are

the reacting species.24

Substitution

Reactions

of

Complexes.-The

temperature- jump method

has

proved valuable for studying kinetics of formation of complexes.

Iron(rr) reacts with nitric oxide at approximately the same rate

as

with

lJ0-phenanthroline or 2,2'-bipyridyl.

25

In formation of a-alanine com-

plexes of nickel(=) and cobalt(@ the rate-determining step

is

the

loss

of

a

water molecule, but the kinetics

of

formation of the manganese(n) complex

with B-alanine are consistent

with

rate-controlling ring closure.a6 Tempera-

ture-jump

27

and pressure-jump

28

studies

of

the reaction of nickel(=) with

malonate give similar results; the rate-determining step

is

the loss

of

water

from the nickel cation followed by reaction with malonate or hydrogen

malonate ion.

This

mechanism

is

the same as for the cobalt(@-malonate

reaction.29 Temperature- jump studies

of

the reaction

of

magnesium(n)

with oxine also indicate parallel reactions

of

the metal

ion

with ligand and

with protonated ligand.30

The equilibrium

Co3+

+

C1-

+

CoC12+ in hydrochloric acid has been

investigated by the stopped-flow method.s1 The forward reaction

is

inter-

esting

as

a rare example of

a

reaction of aquated cobalt(m). Formation of

the mono-acetylacetone (acac) complex

of

iron(m)

in

acid solution

32

occurs,

as

in

the malonate and oxine examples above, by parallel reactions of acac

and acac.€€+

with

FeSf or with Fe(OH)2+.

But

kinetics

of

reaction

of

copper(=) with acetylacetone indicate reaction only with the unprotonated

ligand.s3 Rates of formation

of

terpyridyl complexes of

first-row

transition

metals are similar to rates of formation

of

the respective 1,lO-phenanthroline,

2,2'-

bipyridyl, and pyridine complexes, which implies that attachment

of

the first nitrogen is the kinetically important stage for each

of

these ligands.

The stability constants of the monoterpyridyl complexes are dictated

by

rates

of

dissociation rather than

of

formation.34

Replacement of water

molecules by diethylenetriamine

(as

dien.H+) or nitrilotriacetate

(N'I'AS-)

z2

N.

A.

Daugherty,

J.

Amer. Chem.

SOC.,

1965,

87,

5026.

2s

F.

B.

Baker,

w.

D.

Brewer, and

T.

W.

Newton,

Inorg.

Chem.,

1966,

5,

1294.

84

R.

W. Chlebek and

M.

W. Lister,

Cunud.

J.

Chem.,

1966,

44,

437.

25

K.

Kusth,

I.

A.

Taub, and

E.

Weinstock,

Inorg.

Chem.,

1966,

5,

1079.

26

K.

Kusth,

R.

F.

Pasternak, and

E.

M.

Weinstock,

J.

Amer.

Chem.

SOC.,

1966,

27

F.

P. Cavasino,

J.

Phys. Chem.,

1965,

69,

4380.

28

H.

Hoffman and

J.

Stuehr,

J.

Phys.

Chem.,

1966,

70,

955.

28

F.

p.

Cavasho,

RiceTCa

SC~.,

1965,

8A,

1120.

50

D.

N.

Hague and

M.

Eigen,

Trans. Paraday

soc.,

1966,

62,

1236.

31

T.

J.

Conocchioli,

G.

H.

Nancollas, and

N.

Sutin,

Inorg.

Chem.,

1966,

5,

1.

82

W.

K.

Ong and

R.

H.

Prince,

J.

Chem.

SOC.

(A),

1966,

458.

33

R.

c.

&rile,

M.

Cefola,

P.

8.

Gentile, and

A.

V.

Celiano,

J.

Phys. Chem.,

1966,

a4

R.

H.

Holyer,

C.

D.

Hubbard,

S.

F.

A.

Kettle,

and

R.

G.

Wilkins,

InoTg.

Chem.,

88,

4610.

70,

1358.

1966,

5,

622.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

BURGESS

:

KINETICS

OF

INORGANIC REACTIONS

133

in

[Ni(0H2),L]2+

(L

=

substituted 1,lO-phenanthroline) occurs at rates

whose logarithms correlate

with

Hammett

Q

constants for the respective

substituents.

This

shows effective transmission of substituent effects across

both ligand molecule and metal atom

to

the reaction site. The difference

in electrostatic interaction accounts for the very much faster reaction

of

[Ni(OH2),L]2+ with NTA3- than with dien.

H+.35

The unwrapping of a multidentate ligand from one metal ion and

its

transfer to another has been studied for copper(n)-EDTA reacting with

nickel(=) and zinc(=) tetraethylenepentamine complexes,36 with zinc(=) in

the presence

of

hydroxide, acetate, and azide ions,S7 and for cobalt(n)-EDTA

with nickel@)

.38

Dissociation of complexes of EDTA derivatives has also

been studied, €or instance mercury(rr)-trans-

1,2-diaminocyclohexanetetra-

acetate in acid solution;3Q also cobalt@)-EDTA and cobalt(m)-hydroxy-

ethylethylenediaminetriacetate

in

acid solution

4O

and in the presence

of

thaUium(m).41 The mechanism of EDTA exchange in solutions

of

its

calcium complex involves several paths, the relative importance of which

depends strongly on

pH.d2

Ligand exchange reactions for tetra-ligand

complexes

of

zirconium, hafnium, and thorium with acetylacetone and

trifluoroacetylacetone have been investigated by n.m

.r.

spectros~opy.~~

The

dependence of racemisation rates

of

[Cr(

02C-C02)3]3-

on the nature

of

the complementary alkali metal cation in solution suggests an inter-

mediate in which an oxalate is bonded by

only

one oxygen to the chromium.44

Hydrolysis rates of [Ni(aca~),],~~ and

of

[VO(acac),] and [Be(aca~)~],~~ at

varying acid concentration, imply that protonation

of

unidentate acetyl-

acetone molecules

is

an important factor in the mechanism,

but

kinetics

of

aquation and

lSO

exchange for [Cr(acac),] show

no

evidence for a significant

contribution from protonation

of

unidentate ligand molecules.47

There

is

still

much

work

on reactions

of

complexes

of

the penta-

amrninecobalt(n1) type.

Gay

and Lalor

48

were

not

able to distinguish

between

8,lC.B

and

SN2P

mechanisms for hydroxide reaction

with

[Co(NH3),(NCS)]2+

or

[Cr(NH,),(NCS)J2+, but Banerjea and das

Gupta

4Q

favour the

&2IP

mechanism for base hydrolysis of the former.

For

re-

actions

of

[Co(en),LX]"+

(L

=

OH,

NO2,

Cl,

or an amine; en

=

ethylene-

diamine

or

one of its substituted derivatives) kinetics of reactions under

various conditions, deuterium isotope effects, and steric effects all indicate

85

R.

K.

Steinhaus

and

D.

W.

Margerum,

J.

Amy.

Chern.

SOC.,

1966,

88,

441.

36

D.

W.

Margerum and

J.

D.

Carr,

J.

Amer.

Chem.

SOC.,

1966,

88,

1639, 1645.

37

D.

W.

Margerum,

B.

A. Zabin, and

D.

L.

Janes,

Inorg.

Chem.,

1966,

5,

250.

38

T.

R.

Bhat,

D.

Radhamma, and J. Shankar,

Inorg.

Chem.,

1966,

5,

1132.

38

D.

1;.

Janes and

D.

W.

Margerum,

Inorg.

Chem.,

1966,

5,

1135.

40

S.

P.

Tanner and

W.

C.

E.

Higginson,

J.

Chem.

SOC.

(A),

1966, 537.

41

S.

P.

Tanner and

W.

C.

E.

Higginson,

J.

Chem.

SOC.

(A),

1966,

59.

42

R.

J.

Kula

and

G.

H.

Reed,

Analyt.

Chem.,

1966,

38,

697.

43

A.

C.

Adams and

E.

M.

Larsen,

Inorg.

Chem.,

1966,

5,

228, 814;

T.

J.

Pinnavaia

44

J.

A.

Kernohan,

A.

L.

Odell, R.

W.

Olliff, and

F.

B.

Seaton,

Nutwe,

1966,

209,

45

R.

G.

Pearson and

J.

W.

Moore,

Inorg.

Chem.,

1966,

5,

1523.

R.

G.

Pearson and

J.

W.

Moore,

Inorg.

Chem.,

1966,

5,

1528.

47

J.

Agett

and A.

L.

Odell,

J.

Chem.

SOC.

(A),

1966,

1820.

46

D.

L.

Gay and

G.

C.

Lalor,

J.

Chern.

SOC.

(A),

1966, 1179.

4Q

D.

Banerjea and

T.

P.

das

Gupta,

J.

InoTg.

Nuclear

Chem.,

1966,

28.

1667.

and

R.

C. Fay,

ibid.,

p.

233.

906.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

134

INORGANIC CHEMISTRY

&11P

or

&21P

mechanisms, never

XNlCB.50

Ion-pairing has

a

marked

effect on the rate

of

aquation of [Cr(NH,),Cll2+ in the presence of sulphate,

nitrate,

or

several organic anions; faster rates in the presence

of

these ions

are ascribed to enhanced reactivity

of

ion-~airs.5~ Kinetics and products

of

base hydrolysis of [CO(NH,),X]~+

(X

=

C1, Br,

I,

NO,)

in solutions contain-

ing added ions,

e.g.,

NCS-,

SO4,-,

can

be

explained much more

readily by an

SNICB

than by an

5,2

but kinetics

of

cyanide

exchange with [Co(en),(SO,)(CN)] seem inconsistent with an

SNlcB

mech-

ani~rn.~~ Kinetic studies

of

this type

in

non-aqueous solvents are yielding

results but

it

is

still too early to draw definite

conclusion^.^^

Both

cis-

and trans-[Co( en),(NO,) (NCS)]

+

and [Co(en),(NO,) (NH9)I2

+,

in

acid solution, aquate

by

an

SN1C.A

mechanism rather than the

SN2CA

mechanism more usually found for cobalt(m), rhodium(rn), and iridium(m)

complexes of

this

type.55

Several

other examples

of

the importance

of

protonation of nitro groups

in

acid aquation have been reported, for the

[Co(NR,),(NO,)]

+,

[

Co(

NH,),(NO,),]

+,

and

[Co

(

en),(NO,),]

+

cations.

56

Reactions

of

[

Co

(NH,)

(OH,)]

+

and

[Co

(en)

,

(OH,)

,]

+

with cyanat e have

been studied by tracer experiments. The product carbamato-complex is

formed from the former without breaking the cobalt-oxygen bond, and

in

the [Co(en),(CO,)]+

from

the latter the carbonato ligand contains one oxygen

atom from the water originally on the cobalt, one from the cyanate, and

one from the solvent.67

Rates of halogen exchange

for

[Rh(NH3),XI2+ and

[:Ir(NH3)5X]2+

are

in

the same order as rates for the analogous halogenopenta-amminecobalt(m)

complexes

58

and parallel ligand-field strengths, but reaction rates

of

[Rh(NH3),XI2+ with hydroxide are in the opposite order.59

A

significant

trans effect, both on rates and on actimtion energies, has been reported

for trans-[Rh(en),X,]+ reacting with various

X-.

Results imply

a

wide

variation in the importance of

Rh

.

.

. OH2

bonding in the transition states

for different pairs

of

halogens as

X

and Reaction

of

[Rh(OH,)J3+

with chloride involves the initial rate-determining loss of one water molecule

;

the marked inverse dependence of rate on

pH

is due to the greater reactivity

of [Rh(OH2),(0E)]2+ than

of

the hexa-squo ion.61

Further examples of square-planar complexes which exhibit kinetic

behaviour characteristic

of

octahedral complexes have been reported.

In

So

S.

C.

Chan and

F.

Leh,

J.

Chem.

SOC.

(A),

1966, 126, 129, 134, 138;

S.

C.

man,

ibid.,

pp.

142, 1124, 1310.

61

J.

B. Walker and

C.

B.

Monk,

J.

Chem.

SOC.

(A),

1966, 1372.

62

D.

A.

Buckingham,

I. I.

Olsen, and A.

M.

Sargeson,

J.

Amer. Chem.

SOC.,

1966,

53

E.

Campi,

C.

Paradisi,

G.

Schiavon,

and

M.

L.

Tobe,

Chem. Comm.,

1966, 682.

64

E.g.,

B.

Bosnich,

J.

Ferguson, and

M.

L.

Tobe,

J.

Chem.

SOC.

(A),

1966, 1636.

55

R.

V.

Bradley,

E.

0.

Greaves, and

P.

J.

Staples,

J.

Chem.

SOC.

(A),

1966, 986.

68

G.

C.

Lalor,

J.

Chem.

SOC.

(A),

1966, 1;

D.

G.

Lambed and

J.

G.

Meson,

J.

Amer.

Chem.

SOC.,

1966,

88,

1633, 1637;

U.

D.

Gomwalk

and A. McAuley,

J.

Chem.

SOC.

(A),

1966, 1692, 1694.

57

A.

M.

Sargeson and

€3.

Taube,

Inorg.

Chem.,

1966,

5,

1094.

68

G.

B. Scmidt,

2.

phys. Chem. (Frankfurt),

1966,

50,

222.

59

0.

W.

Bushnell,

G.

C.

Lalor, and

E.

A. Moelqm-Hughes,

J.

Chem.

SOC.

(A),

60

H.

L.

Bott,

E.

J.

Bounsall, and

A.

J.

Poci,

J.

Chem.

Soc.

(A),

1966, 1275.

61

K.

Swaminathan and

G.

M.

Harrsi,

J.

Amer. Chem.

SOC.,

1966,

88,

4411.

88,5443.

1966, 719.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

BURGESS

:

KINETICS

OF

INORGANIC REACTIONS

135

palladium(=) complexes of N-alkyltriamines bulky alkyl groups lead to such

"pseudo-octahedral

"

behaviour. Hydroxide ion catalysis has been demon-

strated for these complexes and explained by

a

CB

mechanism;

this

is the

fist example of hydroxide catalysis in a square-planar system.62

Pseudo-

octahedral behaviour is also found

63

in reactions of the

gold(m)

complex

[AU(l?h4dien-H)X](PF6), where Et,dien-H represents the anion formed by

removal

of

a

proton from

tetraethyldiethylenetriamine,

but the species

[Au(dien)ClI2+, which lacks the sterically-interfering ethyl groups, exhibits

normal square-planar kinetic behaviour.

The normal rate law also applies

to

reactions of [AuC13L] (L

=

heterocyclic nitrogen base) with chloride,

azide, and nitrite,64 and to the reverse reaction

of

[AuClJ- with

L.65

The

[AuCl,L] reactions exhibit marked nucleophilic discrimination, and second-

order rate constants depend greatly on the nature of the substrate and

entering group.

Rate constants

for

reaction with chloride are linearly related

to the basicity of the leaving group.

Rate constants for reaction of

[Pt(bipy)Cl,] ~th aliphatic amines and pyridines are linearly related to the

basicity of tbe entering group,66 though basicity plays a smaller role in deter-

mining reactivity

in

platinum(@ than in gold@) complexes. Rate con-

stants, and so,me

AH$

and

AS$

values, have been reported for many reactions

of

[PtL,X,]

(L

=

nitrogen

or

phosphorus base). Complexes where

L

=

PEt,

have proved especially useful as they shorn

high

nucleophilic discrimination.

Results are discussed in terms of ligand polarisabilities and solvation

effects.67 Although the rate law for hydroxide reaction with

trans-

pt(

H2N*CH,~CH2*OB),C1,] takes the form normal for square-planar species,

direct attack of hydroxide at platinum seems less likely than an anchimeric

assistance mechanism.6g Isomerisationrates

for

[Pd(NCS)L]

+

+

[Pd(SCN)L]+

[L

=

(Et,N*CH,*CH,),NH], and reaction rates for both isomers with brom-

ide, indicate that

this

isomerisation is inter- rather than intra-molecular.6*

The

trans

effect in palladium@) complexes has been studied for carbon

monoxide reaction with [PdX,IZ-

(X

=

halide,

NO,,

NCS,

CN).

These

and earlier resnlts lead to the same

trans

effect series

as

established for

platinum(@

Kinetics of cleavage of halogen-bridged platinum(

n)

com-

plexes by amines have been compared with those of amine attack on normal

unbridged platinum(n) complexes.

71

Ca,rbonyls.-Kinetics

of

carbon monoxide exchange,

and

of

triphenyl-

phosphine reaction, with nickel carbonyl are fist-order

in

carbonyl and

zero-

order in

CO

or

PPh,, and the reactions occur at similar rates in toluene

62

W.

H.

Baddley and

F.

Basolo,

J.

Amer.

Chem.

SOC.,

1966,

88,

2944.

63

C.

F.

Weick and

F.

Basolo,

Inorg.

Chem.,

1966,

5,

576.

64

L.

Cattalini and

M.

L.

Tobe,

Inorg.

Chem.,

1966,

5,

1145.

65

L.

Cattalini,

M.

Nicolini, and

A.

Orio,

Inorg.

Chem.,

1966,

5,

1674.

66

L.

Cattalini,

A.

Orio, and

A.

Doni,

Inorg.

Chem.,

1966,

5,

1517.

67

G.

Faraone,

U.

BeUuco,

V.

Ricevuto, and

R.

Ettorre,

J.

Inorg.

Nuclear Chem.,

1966,

28,

863;

U.

Belluco,

A.

Orio,

and

M.

Martelli,

Inorg.

Chenz.,

1966,

5,

1370,

and

references therein.

68

F.

Basolo and

K.

H.

Stephen,

Inorg.

Nuclear

Chem. Letters,

1966,

2,

23.

F.

Basolo,

W.

H.

Baddley, end

K.

J.

Weidenbaum,

J.

Amer.

Chem.

SOC.,

1966.

7O

A.

B.

Fasman,

G.

G.

Kutyukov,

and

D.

V.

Sokol'skii,

Russ.

J.

Inorg.

Chem.,

7l

R.

G.

Pearson

and

M. M.

Muir,

J.

Amer.

Chem.

SOC.,

1966,

88,

2163.

88,

1576.

1965,

10,

727.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

136

INORGANIC

CHEMISTRY

at

0"c.

It

was therefore assumed that these reactions had

a

common rate-

determining

step,

the

loss

of

a

molecule of

CO

from the carbonyl. Enthlpies

and entropies

of

activation

€or

the two reactions have now been shown

to

differ greatly, implying more complicated mechanisms.72 Results have also

been published for similar reactions of Hg[Co(CO),], and related c0mpounds.7~

Werner and

Prinz

v4

found reactions

of

molybdenum hexacarbonyl with

benzene derivatives, amines, and

phosphines

to be first-order

in

carbonyl

and

zero-order

in

base, although rates did depend on the nature

of

the

entering base. Angelici and Graham,75 working at higher base concentra-

tions, showed that the

full

rate-law was: rate

=

E,[Mo(CO),]+E,[Mo(CO),]

[base]. The second-order term represents

Sx2

attack by the base, but

whether

at

molybdenum

or

carbon

is

not

known.

In

compounds

Mo(CO),L,

(L

=

toluene, p-xylene, mesitylene) replacement of

L

by PCl,,

PPhCl,,

or

P(n-C4Hg)3 follows

simple

second-order kinetics.76

Reaction

of

Co(CO),(NO) with phosphines, arsines,

or

nitrogen bases

itJ

second-order, in contrast to

analogous

reactions

of

isoelectronic

Ni(Co),.'?

There is

a

similar difference

in

kinetic behaviour between reactions

of

the

isoelectronic compounds

Co(CO),(NO)L

and

Ni(

CO),L

[L

=

Asph,,

P(OR),,

Decomposition of cobalt hydrogen carbonyl is a simpl~ second-order

rea~tion.'~ Replacement of carbon monoxide

in

n-cyclopentadienylrhodium

dicarbonyl by phosphine, phosphites, and isonitriles

is

also second-order.m

Addition

of

water, oxygen,

or

methyl iodide to trans-[Ir(CO)(PPh,),X] is

again second-order

;

the activation parameters give some clues to the natures

of the transition states.81

Typical

Elements.-Decompositions

of

nonaborane-15 and octaborane-12

are first-order.82 Reactions

of

the type PhBC1, plus 2,4-dinifronaphthyl-

amine show second-order kinetics and are thought to occur by an

SN2

mechanism.83 The mechanism

of

decomposition

84

of BH,,PF, and similar

adducts is similar to that

of

BIE,,CO, that is

BH,,L

+

BH,

+

L

followed

by

BH,

+

BH,,L

---f

B2H6

+

L.

Alkaline hydrolysis of

BF,,ONMe,,

~EI

of

BF,,amine adducts,

is

first-order, independent

of

hydroxide concentra-

tion

;a5

alkaline hydrolysis of SO,,NEt,

is

second-order, which

is

consistent

with nucleophilic attack by

OH-

at sulphur.86 Kinetics of hydroxide

reaction with difluoramine,

HNF,,

are also second-order

;

the mechanism

L.

R.

Kangas,

R.

F.

Heck,

P.

M.

Henry,

S.

Breitschaft,

E.

M.

Thorsteinson,

and

78

S.

Breitschaft and

B.

Basolo,

J.

Amer.

Chem.

SOC.,

1966, 88, 2702.

74

H.

Werner and

R.

Prinz,

J.

Organometallic Chem.,

1966,

5,

79;

H.

Werner,

ibid.,

75

R.

J.

Angelici and

J.

R.

Graham,

J.

Amer. Chem.

SOC.,

1966,

88,

3658.

76

F.

Zingales,

A.

Chiesa,

and

F.

Basolo,

J.

Amer. Chem.

SOC.,

1966, 88, 2707.

77

R.

J.

Mawby,

D.

Morris,

E.

M.

Thorsteinson, and

F.

Basolo,

Inorg.

Chem.,

1966,

5, 27;

E.

M.

Thorsteinson and

F.

Basolo,

J.

Amer. Chem.

SOC.,

1966,

88,

3929.

78

E.

M.

Thorsteinson and

F.

Basolo,

Imrg.

Chem.,

1966, 5, 1691.

7s

K.

H.

Brandes and

H.

B.

Jonassen,

2.

anorg.

Chem.,

1966,

343,

215.

H.

G.

Schuster-Woldan and

F.

Basolo,

J.

Amer. Chem.

SOC.,

1966,

88,

1657.

81

P.

B.

Chock and

J.

Halpern,

J.

Amer.

Chm.

SOC.,

1966,

88,

3511.

82

J.

F.

Ditter,

J.

R.

Spielman, and

R.

E.

Williams,

Inorg.

Chem., 1966,

5,

118.

84

A.

B.

Burg

and Yuan-Chin Fu,

J.

Amer.

Chem.

SOC.,

1966, 88, 1147.

8s

I. G.

Ryss

and

S.

L.

Idel's,

Rust?.

J.

Inorg.

Chem.,

1966,

10,

424.

86

I.

G.

Ryss

and

L.

P.

Bogdanova,

Rws.

J.

Inorg.

Chem., 1965,lO. 91.

F.

Basolo,

J.

Amer. Chem.

SOC.,

1966,

88,

2334.

p.

100.

J.

C.

Lockhart,

J.

Chem.

SOC.

(A),

1966,

809.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

BURGESS

:

KINETICS

OF

INORGANIC REACTIONS

137

may be

SN2,

as for

NF,,

or assisted

XN1,

but does not involve ionisation

of

HNF2.s7

Rates of racemisation and deuteriation of the complex cation

[Co(NH3),(CH3*NH-CH,.C0,)12'

suggest retention of configuration about

the sarcosine-N atom for a kinetically significant, time after

loss

of the

proton.

Cleavage of Sn-Sn bonds

in

hexaphenylditin has been investigated by

reaction with iodine. The second-order kinetics, e.s.r., and DPPH reaction

experiments give no evidence for

a

significant contribution from radical

reacti0ns.8~ Nor is there any evidence

for

the generation

of

radicals during

the iodination of several other ditin compounds in a variety of

except from hexamethylditin under the most favourable

condition^.^^

Pre-

equilibrium with solvent followed by formation of an acyclic four-centre

transition state seems the more usual mechani~rn.~~ Tin-phenyl bond

cleavage in the reaction

of

Ph2SnC1, with oxine takes place both by simple

bond breaking and by formation and decomposition

of

an adduct

Ph,SnCl,,(~xine),.~~ The mechanism of reaction

of

tetra-alkyl lead com-

pounds with iodine is

SE2

substitution at carbon; results in

a

variety

of

solvents indicate significant solvation in the transition state.93

Anions.-Kinetics of hydrolysis

of

pyropho~phite,9~ pyrophosphate~,~~

and peroxopho~phates,~~

of

alcoholysis

of

polyphosphoric acidsYg7 and

of

reaction

of

peroxo-di-phosphate with iodine have been reported.gs

In

all

cases the variation

of

concentrations of variously protonated species at

different pH values makes deduction of complete reaction mechanisms

hazardous if not impossible. Similar difficulties are encountered in halide-

halate reactions,

e.g.,

iodide-cWorite.99

The most informative work has

been the investigation

of

base hydrolysis

of

the dichromate ion by water,

ammonia, hydroxide ion, and 2,6-lutidine.

lo0

The order

of

reactivity

parallels basicity if due allowance is made

for

electrostatic repulsion and

for

steric effects in the cases

of

hydroxide and lutidine, respectively.

The

behaviour of Cr,0,2- is very similar to that

of

S,0,2-

A.

D.

Craig and

G.

A.

Ward,

J.

Amer. Chem. SOC.,

1966,

88,

4526.

88

B.

Halpern,

A.

M.

Sargeson, and

K. R.

Turnbull,

J.

Amer.

Chem.

SOC.,

1966,

88,

D.

N.

Hague and

R.

H.

Prince,

J.

Inorg. Nuclear Chem.,

1966,

28,

1039.

O0

G. Tagliavini,

S.

Faleschini,

G.

Pilloni, and G. Plazzogna,

J.

OrganometaUk

91

H.

C.

Clark,

J.

D.

Cotton, and

J.

H.

Tsai,

Canad.

J.

Chem., 1966,

44,

903.

OS

D.

F.

Martin and

R.

D.

Walton,

J.

OrganometaUic Chem.,

1966,

5,

57.

OS

L.

Riccoboni, G. Pilloni,

G.

Plazzogna, and G. Tagliavini,

J.

ElectroanaZyt.

Chem.

O4

R.

E.

Mesmer and

R.

L.

Carroll,

J.

Amer. Chem.

SOC.,

1966,

88,

1381.

O5

R.

P.

Mitra,

H.

C.

Malhotra, and

D.

V.

S.

Jain,

Trans.

Faraday

SOC.,

1966,

62,

O6

S. H.

Goh,

R.

B.

Heslop, and

J.

W.

Lethbridge,

J.

Chem.

SOC.

(A),

1966, 1302.

97

F.

B.

Clarke

and

J.

W. Lyons,

J.

Amer. Chem.

Soc., 1966,

88,

4401.

98

A.

Indelli and

P.

L.

Bonora,

J.

Amer.

Chem.

SOC.,

1966,

88,

924.

99

J.

de Meeus and

J.

SigalIa,

J.

Chim. phys.,

1966,

63,

453.

4630.

Chem., 1966, 5, 136.

Interfacial Electrochem.,

1966,

11,

340.

173;

C.

A.

Bunton and

H.

Chaimovich,

Inorg. Chem.,

1965,

4,

1763.

loo

P. Moore,

S.

F.

A.

Kettle, and

R.

G.

Wilkins,

Inorg. Chern.,

1966,

5,

220.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

3.

THE

TYPICAL

ELEMENTS,

By

A.

J.

Downs

(Inorganic Chenzistry

Laboratory,

South Park8 Road,

Oxford)

E.

A.

V.

Ebsworth

and

J.

J.

Turner

(

Univer&ty Chemical Laboratory, Lensfceld

Road,

Cambridge)

IN

the past year there has been no particularly important advance in the

chemistry of the typical elements.

A

series

of

papers deals with the electro-

chemistry of organometallic compounds and the electrochemical formation

of

metal-metal b0nds.l Other

work

implies that two commonly used methods

of

assessing the strengths of donor-acceptor bonds are of doubtful validity

:

manometric investigations of some sulphide adducts do not support

a

scale

of

donor strengths based on adduct volatility;2a the variations

in

the

(CkO)

stretching frequency

of

perinaphthenone accompanying reaction with various

acceptors are not directly related to the formation constants

of

the com-

plexes.2b

For

adducts of several Lewis acids, the relative strengths

of

bases

appear to depend principally on the strength

of

the acid, and not neces-

sarily

on

supplementary rc-bonding.2c The concept of the donor number has

been introduced into discussions

of

non-aqueous solvents.2d

Reviews have been published on the following topics

:

the structures and

reactions of carbanionic organometallic compounds

3a

of the elements

of

Groups

I-VI

;

the preparation

of

methylmetal compounds using fused

salts

;

3b

the preparation and properties

of

pentafluorophenyl compounds

of

main

group

and transition elements

;3c

organometnllic azides

;3d

inorganic

analogues

of

carbenes

;3*

five

co-ordination

;3t

the n.m.r. spectra

of

organo-

metallic compounds.39

A

monograph dealing with the hydrogen compounds

of

the metallic elements

40

has appeared;

a

collection

of

articles about non-

aqueous solvent systems has been p~blished,~b and

a

substantial study of

inorganic and general chemistry in liquid ammonia4c represents Part

I

of

Volume

I

of

a

series.

A

collection of data relating to the appearance poten-

(a)

R.

E. Dessy,

W.

Kitching, and

T.

Chivers,

J.

Amer.

Chem.Soc.,

1966,88,453;

(b)

R.

E.

Dessy,

T.

Chivers, and

W.

Kitching,

ibid.,

p.

467;

(c)R.

E.

Dessy,

P.

M.

Weissman,

and

R.

L.

Pohl,

ibid.,

p.

5117;

(d)

R.

E.

Dessyand

P.

M.

Weissman,

ibid.,

pp.

5124, 5129.

a

(a)

H.

A.

Norris,

N.

I.

Kulevsky,

31.

Tamres, and

S.

Searles,

Inorg.

Chem.,

1966,

5,

124;

(b)

A. Mohammed and

D.

P.

N. Satchell,

Chem.

and

Id.,

1966, 2013;

(c)

D.

E.

Young, G.

E.

McAchan,

and

S.

G.

Shore,

J.

Amer. Chem. doc.,

1966,

88,

4390;

(d)

V.

Gutmaun and

E.

Wychera,

Inorg.

Nzcclear

Chem. Letters,

1966,

2,

257.

(a)

W.

Tochtermann,

Angew. Chem., Internat.

Edn.,

1966,

5,

351;

(b)

W.

Sunder-

meyer

and

W.

Verbeek,

ibid.,

p.

1

;

(c)

R.

D.

Chambers and

T.

Chivers,

Organometallic

Chem.

Rev.,

196G,

1,

279;

(d)

J.

S.

Thayer,

ibid.,

p.

157;

(e)

0.

M.

Nefedov and

M.

N.

Manakov,

Angew.

Chem.,

Internat. Edn.,

1966,

5,

1021;

(f)

E.

L.

Muetterties and

R.

A.

Schunn,

Quart.

Rev.,

1966,

20,

245;

(9)

M.

L.

Maddox,

S.

L.

Stafford, and

H.

D.

Kaesz,

Adu. Organometallic Chem.,

1965,

3,

1.

4

(a)

I<.

M.

Mackay,

"

Hydrogen Compounds

4:

the Metallic Elements,"

E.

an:

F.

N.

Spon, London,

1966;

(b)

T.

C.

Waddington,

Academic Press,

1965;

(c)

J.

Jander, Chemistry

in

Liquid Ammonia-I. Inorganic

and General Chemistry

in

Liquid Ammonia," Vieweg, Brunswick, and Interscience,

New York-London,

1966.

Non-aqueous Solvent Systems,

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

DOWNS,

EBSWORTH

AND

TURNER:

THE

TYPICAL

ELEMENTS

139

tials

of

volatile inorganic compounds has been made,5a and

to

the Sadtler

collection of the infrared spectra of

600

inorganic compounds5b have been

added the spectra

of

400

organometallic derivatives.5c

Group

0.-Noble-gas chemistry has been reviewed,6 and noble-gas rad-

iation chemistry discussed.' Krypton difjluoride can

be

prepared by the

exposure

of

a

krypton-fluorine mixture fa daylight;gu E(Kr-F) has the

surprisingly low value

8b

of

12 kcal.mole-1. There is no evidenceg for the

formation

of

krypton-oxygen compounds

from

the ra.dioactive decay of

K83Br0,.

The existence

of

XeF, and XeF, has not been confirmed.1°

Electric discharge

in

a gas mixture

of

Xe,

F,,

and CCl,

(or

SiC1,)

gives

colourless crystals whose

vapour

shows a mass spectrum containing XeC1-;

the formation

of

XeC1, is deduced;lla liquid chlorine and gaseous Xe under

pressure slowly formed crysta1s,llb perhaps

of

XeCI,. Further investi-

gation of the Xe-PtF5 system

l2

has led

to

the preparation

of

XeF,+PtF,-,

the XeF5+ ion being approximately square-pyramidal [Xe-F(4)

=

1.90

8;

Xe-F(1)

=

1-77

8;

F(4)-Xe-F(1)

=

83'1.

Heat-capacity data suggest

that there are three structural modifications

l3

of

solid XeF,; the non-

octahedral structure

of

gaseous XeF, has been ~~Ilfirrned,~~ and the structure

discussed theoretically.15 The magnetic susceptibility16

9

l7

of

solid XeF,

indicates the absence

of

a lom-lying triplet state; the

l9F

n.m.r. spec-

trum

l7

of

solid XeF, and the

I'O

n.m.r. spectrum

l8

of

liquid XeOF,

have been examined. Further reported complexes are 4XeF,,SnF4,1g

2XeF,,VF,, 2XeOF,,VF5,20 XeOF,,CsF, 2XeOF4,3RbF, Xe0F4,3KF,

XeOF4,2SbF,,

21

XeFG,2NOF, and XeOF,,NOF

;

infrared spectra suggest

(a)

H.

J.

Svec,

"Mass

Spectrometry,"

NATO

Adv. Study Inst. Glasgow,

1964

(publ.

1965);

(b)

"

High Resolution Spectra

of

Inorganics and Related Compounds,"

Sadtler Research Laboratories, Philadelphia,

1965;

(c)

"

Infrared Grating Spectra

of

Organometallic Compounds," Sadtler Research Laboratories, Philadelphia,

1966.

R.

Hoppe,

Fortschr. Chem.

Forsch.,

1965,

5,

213;

A.

B.

Neiding,

Russ.

Chem.

Rev.,

1965,

34,

403;

G.

J.

Moody and

J.

D.

It.

Thomas,

Rev. Pure

AppZ.

Chem.,

1966,

16,

1.

J.

P.

Adloff,

Radiochim. Acta,

1966,

6,

1;

G.

J.

Moody and

J.

D.

R.

Thomas,

Nature,

1965,

206,

613.

*

(a)

L.

V.

Streng and

A.

G.

Streng,

Inorg.

Clzem.,

1966,

5,

328;

(b)

S.

R.

Gunn,

J.

Amer.

Chem.Xoc.,

1966,

88,

5924.

A.

N.

Murin,

T7.

D.

Nefedov,

I.

S.

Kirin,

S.

A.

Grachev, Yu.

K.

Gusev, and

G.

N.

Shaplzin,J.

Gen. Chem.

(U.S.S.R.),

1965,

35,

2126.

lo

R.

Weinstock,

E.

E.

Weaver, and

C.

P.

Knop,

Inorg.

Chem.,

1966,

5,

2189.

l1

(a)

H.

Meinert,

2.

Chem.,

1966,

6,

71;

(b)

S.

F.

a.

Kettle,

Chem.

and

Ind,,

1966,

l2

N.

Bartlett,

F.

Einstein,

D.

F.

Stewart, and

J.

Trotter,

Chem.

Comm.,

1966, 550.

l3

J.

G.

Mah,

F.

SchrcL?er, 2nd

D.

W.

Osborne,

Inorg.

Nuclear

Chem.

Letters,

1965,

l4

K.

Hedberg,

S.

H.

Peterson, R.

R.

Ryan,

and

B.

VVeinstock,

J.

Clzenz.

Phys.,

l5

R.

D.

Willett,

Theor.

Chim.

Acta,

1966,

6,

186;

L.

S.

Bartell,

Trans.

Amer.

Cryst.

l6 (a)

B.

Volaviiek,

Monatsh.,

1966,

9'7,

1531;

(b)

H.

Selig and

F.

Schreiner,

J.

Chem.

l7

R.

Blinc,

E.

Pirkmajer,

J.

Slivnik, and

I.

ZupenEi6,

J.

Chem. Phys.,

1966,

45,

lS

J.

Shamir,

H.

Selig,

D.

Samuel, and

J.

Reuben,

J.

Amer.

Chem.

Soc.,

1965,

87,

l9

K.

E.

Pullen and

G.

H.

Cady,

Irzorg.

Chem.,

1966,

5,

2057.

2o

G.

J.

Moody and

H.

Selig,

J.

Inorg.

Nuclear

Chem.,

1966,

28,

2429.

a1

H.

Selig,

Inorg.

Chm.,

1966,

5,

183.

1846.

1,

97.

1966,

44,

1726.

ASSOC.,

1966,

2,

134.

Phys.,

1966,

45,

4755.

1488.

2359.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

140

INORGANIC

CHEMISTRY

that the last two contain the

NO+

ion.22 Infrared and X-ray evidence

11~23

indicates that the

Xe0,F-

ion

is

not present

in

CsXe0,F. Mixtures

of

XeF,

and XeF,

in

SbF,

form green solutions

24

which from their e.s.r. spectra may

contain Xe(m). Raman spectra afford no evidence

25

for the formation

of

Xe0,F2 on addition of water to XeOF,

in

liquid

El?;

infrared evidence

for

the formation of XeOF, at

low

temperatures has been presented.26 The

preparations of

CsHXeO,

27

and Am4(Xe0,),,40H,O

28

have been described.

The negative interaction force constant

29

in

KrF,

has

been simply ex-

~lained.~*

Group

1.-More information about alkali metal solutions

in

liquid

ammonia and amines emerges from measurements

of

heats

of

solution

31a

and

electron spin resonance and electronic absorption ~pectra.3~~ One conclu-

sion

31b

is

that the blue diamagnetic species present

in

moderately concen-

trated solutions

is

most satisfactorily represented by (e22-)so1v.

;

in primary

amines31c

RNH2

solvated atoms are present as well

as

solvated electrons, and

the spectroscopic properties are very dependent on

R.

The inversional

motion of the ammonia molecule may be the basis

of

the conduction mechan-

ism

in

dilute solutions

of

lithium

in

liquid ammonia.31d Certain properties

of

dilute alkali metal-ammonia solutions can be explained

32

by

a

model

involving equilibria between the solvated metal cation

M+

and anion

M-,

the solvent

S,

the anion

S-,

and the ion-pairs

M+M-

and

M+S-.

Proton

n.m.r. spectra of liquid ammonia solutions

of

alkali salts reflect ion-solvation,

ion-association, and hydrogen- bonding effects.

33

Magnetic resonances

of

the nuclei 23Na,

39K,

87Rb,

and

la3Cs

in aqueous

alkali salt solutions

34

disclose the following order

of

increasing shielding by

the anions:

I-

<

Br-

<

C1-

<

F-

<

H20

<

NO,-;

overlap repulsive forces

between the closed-shell ions may account for the observed chemical shifts.

Despite the relative insensitivity

to

structural effects, 'Li resonances may

provide information about the solvation

of

Li+ ions

in

solution,35 and about

organolithium exchange rea~tions.~a Broad-line measurements

on

poly-

23

G.

J.

Moody and

H.

Selig,

Inorg. Nuclear

Chem.

Letters,

1966,

2,

319.

23

R.

D.

Peacock,

H.

Selig, and

I.

Sheft,

J.

Inorg.

Nuclear

Chem.,

1966,

28,

2561.

2a

B.

Cohen and

R.

D.

Peacoolr,

J.

lnorg.

Nuclear

Chem.,

1966,

28,

3056.

26

H. H.

Selig,

L.

A.

Quarterman, and

H.

H. Hyman,

J.

Inorg. Nuclear

Chem.,

27

B.

Jaselkis,

T.

M. Spittler, and

J.

L.

Huston,

J.

Amer.

Chem.

Xoc.,

1966,

88,

2s

H.

H.

Claassen,

G.

L.

Goodman,

J.

G. Malm, and

F.

Schreiner,

J.

Chem.

Phys.,

1965,

42,

1229.

ao

C.

A.

Coulson,

J.

Chem.

Phys.,

1966,

44,

468.

31

(a)

T.

R.

Tuttle,

jun.,

C.

Guttman, and

S.

Golden,

J.

Chew.

Phys.,

1966,

45,

2206;

(b)

R.

Catterall and

M.

C.

R. Symons,

J.

Chem.

SOC.

(A),

1966, 13;

(c)

R.

Catterall,

M.

C.

R.

Symons,

and

J.

W.

Tipping,

ibid.,

p.

1529;

(d)

E.

C.

Evers and

F.

R.

Longo,

J.

Phys.

Chem.,

1966,

70,

426.

1966,

28,

2063.

J.

S.

Ogden and

J. J.

Turner,

Chem.

Comm.,

1966, 693.

Y.

Marcus and

D.

Cohen,

Inorg.

Chem.,

1966,

5,

1740.

2149.

32

S.

Golden,

C.

Guttman,

and

T.

R.

Tuttle, jun.,

J.

Chem. Phys.,

1966,

44,

3791.

33

A.

L.

Allred and

R.

N.

Wendriclrs,

J.

Chem.

SOC.

(A),

1966, 778.

34

C.

Deverell and

R.

E.

Richards,

MoZ.

Phys.,

1966,

10,

551.

s5

G.

E.

Maciel,

J.

K.

Hancock,

L.

F.

Lafferty,

P.

A.

Mueller, and

W.

K.

Musker,

Inorg.

Chem.,

1966,

5,

554.

36

L.

M. Seitz and

T.

L.

Brown,

J.

Amer.

Chem.

Soc.,

1966,

88,

2174, 4140;

K.

C.

Williams and

T.

L.

Brown,

{bid.,

p.

4134;

G.

E.

Hartwell and

T.

L.

Brown,

ibid.,

p.

4626.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

DOWNS,

EBSWORTH

AND

TURNER:

THE

TYPICAL

ELEMENTS

141

crystallinelithium compounds

37a

reveal structural effects like the

two

non-

equivalent lithium sites

in

lithium nitride.37b

Organolithium compounds have been reviewed.

38

Kinetic experiments

on

metallation reactions indicate

a9a

that organolithium aggregates can act as

kinetically active species

;

denends on the structure

the extent

of

aggregation in basic solvents

of the organometallic compound.39b Spectro-

scipic data suggest

40

that

in

but-3-enyl-lithium interadion occurs between

vacant orbitals on the hexameric lithium framework and the n-orbitals of the

butene moiety

(1).

The formation

of

specific

organolithium-tetrahydrofuran

complexes is revealed

by

the electronic spectrum of

1

,l-diphenyl-n-hexyl-

lithium,41 the acidity of the

Li+

cation varying with the extent

of

solvation.

Evidence from several sources suggest,s that lithium bromide exists as

tetramers in diethyl ether solution.42 Lithium nitroxide, formed through

reaction

of

lithium atoms and

NO

in solid argon at high dilution, has

a

bent

molecule

43

and is probably LiON rather than

LiNO

(LiON

=

100"

&

10").

Microwave spectra,

44

of

the gaseous hydroxide molecules

CsOH

and

KOH

conform,

however,

to

the linear-molecule pattern, although a

"

quasilinear

"

structure cannot be excluded.

Group

II.-Organoberyllium hydrides, RBeH

(R

=

Me,

Et

or Ph), can

be

prepared as diethyl ether complexes from the appropriate diorgano-

beryllium, beryllium bromide and lithium hydride

;45

the liquid

1

:

1

complex

of methylberyllium hydride is

a

dimer, [MeBeH,Et,O],. Organoberyllium

hydrides and related compounds add to unsaturated systems like olefins,

aldehydes, and ketones;

45

reaction rates are sensitive to the presence

(a)

R.

A.

Bernheim,

I.

L.

Adler,

B.

J.

Lavmy,

D.

C.

Lini,

B.

A.

Scott, and

J.

A.

Dixon,

J.

Chem. Phys.,

1966,

45,

3442;

(b)

S.

0.

Bishop,

P.

J.

Ring,

and

P.

J.

Bray,

ibid.,

p.

1625.

38

T.

L.

Brown,

Adv. Organometallic Chem.,

1965,

3,

365.

39

(a)

T.

L.

Brown,

J.

Organometallic Chem.,

1966,

5,

191;

R.

Waack,

P.

West, and

M.

A. Doran,

Chem. and

Ind.,

1966, 1035;

(b)

R.

Waack and

P.

West,

J.

Organometallic

Chem.,

1966,

5,

188.

40

J.

P.

Oliver,

J.

B.

Smart, and

M.

T.

Emerson,

J.

Amer. Chem.

Xoc., 1966,

88,

2109.

41

R.

Waack,

M.

A.

Doran, and

P.

E.

Stevenson,

J.

Amer. Chem.

Soc.,

1966,

88,

4101.

42

M.

Chabanel,

J.

Chim. phys.,

1966,

63,

1143.

43

W.

L.

S.

Andrews

and

G.

C.

Pimentel,

J.

Chem. Phys.,

1966,

44,

2361.

44

R.

L.

Kuczkowski,

D.

R.

Lide,

jun.,

and

L.

C.

Krisher,

J.

Chem.

Phys.,

1966,

46

N.

A.

Bell

and

G.

E.

Coatea,

J.

Chm.

SOC.

(A),

1966, 1069.

A

44,

3131.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

142

INORGANIC

CHEMISTRY

of

ether and to the site of unsaturation in the organic molecule.

On

the basis

of

n.m.r. spectr0scopy,4~

cis-trans

isomerism

of

the dimer

Me,N(Me)BeH,Be(Me)NMe,

is

indicated. Tetramethyltetrazene reacts with

dialkylberylliums to give both

1

:

1

and

1

:

2

complexes

(Me,N*N=N-NMe2,R2Be)

;

47

pyrolysis

of

the latter leads to polymers of low molecular weight.

The

beryllium derivatives

of

NNN'-

trimet hyle

t

hylenediamine,

2

-met hoxyet hanol,

2 -&met hylaminoethanol, and 2-dimet hylaminoet hanethiol range from

monomers to polymers.48 Spectroscopic properties

of

methylberyllium

compounds such

as

Na2[Me,Be,H,] and trimethylamine and tetramethyl-

ethylenediamine complexes

of

Me,Be are correlated with the structural units

present,49 and a conformationally labile 6-membered ring structure

is

assigned to [MeBeNMe,],. Beryllium borohydride complexes, L,Be(BH,),

(L

=

Et,O,

Me,P,

Me2PH,

Et,P,

Me,", and

Me2NH)

are liquid at room

temperature, and monomeric in benzene.

50

Interaction

of

beryllium acetyl-

acetonats with phosphonitrilic derivatives like Ph2P( O)NPPh,OH produces

both mono- and di-substituted monomeric beryllium phosphonitrilates

[typically

(2)].

51

Ph, ,Ph Ph,

,'Ph

N

I\

/\

Ph Ph Ph

-Ph

CH2

-

Me2NL

,

Me

1

NMe

-

1

2%

NMgS

CH2

-

MeN

L/

'Me

NMe2

-

i"'

CH2

(3)

A

review

of

organomagnesium compounds

52a

emphasises that the consti-

tution

of

Grignard reagents depends on the concentration of the solution

and

the nature

of

the organic group, halogen, and solvent.

Current

views

on

Grignard reagents are radically affected by the ambiguity

52b

of the critical

"

no-exchange

''

experiment involving Mg*Br2 and Et,Mg.

In

dilute ether

solution, R2Mg and MgX,

(R

=

Et

or Ph;

X

=

Br or

I)

react rapidly

and exothermically, giving solutions indistinguishable from those

of

the

corresponding Grignard reagents;52c the main reaction appears to be

:

the equilibrium strongly favouring RMgX.

A

similar equilibrium with

K

m

4

is

consistent

with

the polarographic behaviour

5Zd

of

organomagnesium

species in 1,2-&methoxyethane. In ethereal solutions

of

the pentafluoro-

phenyl Grignard reagent, C,F,MgBr and (C,F,),Mg

(or

species based on these

groupings) coexist and exchange rapidly (on an n.m.r. timescale) at

ca.

R2Mg

+

MgX2

+

ZRMgX,

4c

N.

A.

Bell,

G.

E.

Coates, and

J.

W.

Emsley,

J.

Chem.

SOC.

(A),

1966, 1360.

47

N.

R.

Fetter,

J.

Chem.

SOC.

(A),

1966, 711.

N. A.

Bell,

J.

Chem.

SOC.

(A),

1966,

548.

4D

N.

A.

Bell,

G.

E.

Coates, and

J.

W.

Emsloy,

J.

Chem.

Soc.

(A),

1966, 49.

L.

Banford and

G.

E.

Coates,

J.

Chem.

Soc.

(A),

1966,

274.

61

K. L.

Paciorelr and

R.

H.

Krtttzor,

Inorg. Chem., 1966,

5,

638.

62 (a)

B.

J.

Wakefield,

Organometallic

Chm.

Rev.,

1966,

1,

131;

(b)

R.

E.

Dessy,

S.

E.

I.

Green,

and

R.

M.

Salinger,

Tetrahedron Letters, 1964, 1369;

(c)

M.

B.

Smith

and

W.

E.

Becker,

Tetrahedron, 1966,22,3027;

(d)

T.

Psarras

and

R.

E.

Dessy,

J.

Amer.

Chem.

SOC.,

1966,88, 5132;

(e)

D.

F.

Evans

and

35.

S.

Khan,

Chem.

Comm.,

1966, 67.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

DOWNS,

EBSWORTH

AND

TURNER:

THE

TYPICAL

ELEMENTS

143

90"c.

Complexes

(1

:

1)

of

Me,&lg and Ph,Mg with tetramethylethylene-

diamine and 1,Z-dimethoxyethane, monomeric

in

benzene, have been char-

a~terised,~~ whereas with

trimethylethylenediamine

Me,Mg gives a dimeric

product, probably with the structure

(3).

Of

the several alkylmagnesium

alkoxides recent,ly prepared,54 only those with chain-branching at the carbon

atom

a

to oxygen are tetrameric in benzene; compounds like EtMgOPP and

PriMgOMe under similar conditions have degrees of association

of

7-804,

and secondary aminomagnesium alkyls are dimeric,

e.g.,

priMgNPri,],.

Typical

of

some of the crystalline magnesium alkoxide-ether complexes pre-

pared

54

is

a derivative, which, being dimeric in benzene, probably has the

structure

(4).

For

the gaseous metal dihalide molecules

MX,

(M

=

Be,

Mg,

Ca,

Sr,

Ba;

X

=

F,

CI,

Br,

I)

the observed geometries are correlated

55

with the increas-

ing importance of d-orbitals with increase

of

atomic number. The octa-

hedral MgCl64- and pyramidal MgC1,- ions have been identified by Raman

spectroscopy

56

in

molten MgCl, and MgCl,-KCl, respectively. The

so-

called

''

alkaline-earth metal carbonyls

''

formulated as

M(CO),

are mixtures

of

acetylenediolates, methoxides, and ammonium ~arbonate.~' On the basis

of

conductivity and freezing-point measurements,

it

is

suggested

58

that

dissolution of calcium and strontium in their respective molten halides leads

to an equilibrium

2M2+

+

2e

+

(M2)2+;

(BaJ2+

is, however, comparatively

unstable.

Group

IIL-Boron.

llB

n.m.r. spectroscopy remains a fruitful source

of

stereochemical information

;

recent results include a unique assignment of the

llB

spectra of

1

,2-dicarbaclovododecaborane

59

and 2,4-dicarbaclovohepta-

borane,60 confirmation

61

of

the previously suggested structures

for

B&f8,C0

and

B,H,,PF3,

spectroscopic characterisation

of

various mono- and di-

alkyldiboranes,62 and structural assignments

of

several new polyborane and

carborane systems subsequently

to

be described. Extension

of

the quanti-

tative theory

of

llB

chemical shifts

63

beyond empirical correlations is

53

G.

E.

Coates and

J.

A.

Heslop,

J.

Chem.

SOC.

(A),

1966,

26.

64

G.

E.

Coates and

D.

Ridley,

Chem.

Comm.,

1066, 560.

55

E.

F.

Hayes,

J.

Phys. Chenz.,

1966,

70,

3740.

56

K.

Balasubrahmanyan,

J.

Chem. Phys.,

1966,

44,

3270.

57

W.

Biichner,

Helv.

Chim.

Ada,

1966,

49,

907.

58

A.

S.

Dworkin,

H.

R. Bronstein, and

M.

A.

Bredig,

J.

Phys. Chem.,

1966,

70,

69

J.

A.

Potenza,

W.

N.

Lipscomb,

G.

D.

Vickers, and

H.

Schroeder,

J.

Amer.

6o

T.

Onak,

G.

B.

Dunks,

R.

A.

Beaudet, and

R.

L. Poynter,

J.

Amer.

Chena.

SOC.,

61

A.

D.

Norman

and

R.

Schaeffer,

J.

Amer. Chem.

Soc.,

1966,

88,

1143.

62

H.

H.

Lindner

and

T.

Onak,

J.

Amer. Chem.

SOC.,

1966,

88,

1890.

6s

F.

P.

Boer,

R.

A.

Hegstrom,

M.

D.

Newton,

J.

A.

Potenze,

and

W.

N.

Lipscomb,

2384.

Chem.

SOC.,

1966,

88,

628.

1966,

88,

4622.

J.

Amer.

Chern.

Xoc.,

1966,

88,

6340.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

144

INORGANIC

CHEMISTRY

possible for the icosahedral carboranes for which the shifts are primarily deter-

mined by differences

in

paramagnetic shielding. Systematic surveys of

llB

n.m.r. spectra show that,

in

trigonal boron systems, (i) the chemical shift

is determined principally by the atoms directly bound to boron, and

(ii)

n-

bonding probably contributes to the shielding of the boron.

lH

n.m.r. measurements imply that the order

of

acceptor activity

with

respect to acetonitrile

65a

is BBr,

>

BCl,

>

BF,,

and that the activities

of

B(C,F,),

and

BF,

are comparable.65b Comparison of donor and acceptor

strengths has also been an objective of (i) manometric studies

of

BF,

and

BCl, with sulphide ligands

2a

and

of

BF,,

BH,,

and BMe, with phosphines,66u

(ii) the characterisation of boron halide-phosphorus halide complexes,66b

(iii)

displacement reactions, vapour density, and kinetic studies

of

complexes

of several boron acids? (iv) dissociation pressure measurements

of

adducts

of Me,N and Me,P with 1,3,2-dioxaborolan and 1,3,2-dioxaborinan (implying

that the &membered ring

is

the stronger acid).6Gc Differences in acceptor

ability presumably contribute

to

the variations

in

charge-transfer spectra and

oxidation potentials of metal cyanide adducts Fe(phen),(CN,BX,),

(X

=

Me,

H,

F,

C1,

and Br) wherein the BX, unit apparently decreases metal-ligand

a-bonding and increases n-bonding. Thermochemical estimates

of

the B-0

bond energy

of

the complexes

Y,B,OPX,

(X,

Y

=

C1

or

Br)67 are an order

of

magnitude less than

"

normal

"

B-0

bond energies. New borane adducts

include

a

compound with the probable structure H,B,P,O,,BH,, and

L,BH,

and L,ZBH, species,68b where

L

is

tetramethylethylenediamine,

NN'-

dimethylpiperazine, or triethylenediamine. Anomalous variations in the

dipole moments

of

the amine boranes Me,NH,-,,BH, are attributed

6g

to

the

combined polarising influences of the four ligands on the nitrogen lone-pair.

Recent preparative developments have enlarged the range

of

metal-

boron

compounds. Essentially localised metal-boron bonds presumably

exist

in

the addition compounds L,Rh(CO)X,BY,

(L

=

Ph,P or Ph,As;

X

=

C1

or

Br

;

Y

=

C1

or

Br),7Oa (n-C5H,),MH2,BX, and (n-C5HS),ReH,BX,

(M

=

Mo

or

W;

X

=

F

or Cl),70b and [Cl,M,BX,]-

(M

==

Ge or Sn;

X

=

F

or Cl);?OC the aflhity

of

the cyclopentadienyl metal hydrides and

MCl,-

ions

7oc

for Werent boron acids indicates

''

hard base

"

character for the

metal atoms. Substitution reactions

of

manganese carbonyls lead

to

the

formation

of

Mn-B

bonds in compounds of the type X,B*Mn(C0)4L and

XB[Mn(CO),PPh,J,

(X

=

Ph,

Bu,

C1, NR,,OMe; L

=

CO

or

PPh3);'la

64

J.

E.

De

Moor and

(3.

P. Van

der

Kelen,

J.

Orgartometallic Chem.,

1966, 6,

235;

H.

Noth

and

H.

Vahrenkamp,

Chem. Ber.,

1966,

99,

1049.

65

(a)

J.

M.

Miller and

M.

Onyszchuk,

Cad.

J.

Chem.,

1966,

44,

899;

(b)

A.

0.

Massey and

A.

J.

Park,

J.

Organmetallic

Chem.,

1966,

5,

218.

66

(a)

H.

L.

Morris, M. Tamres, and

S.

Searles,

Inorg.

Chem.,

1966,

5,2156;

(b)

A.

F.

Armington,

J.

R.

Weiner,

and

G.

H.

Moates,

&bid.,

p.

483;

(c)

G.

E.

McAchran and

8.

G.

Shore,

ibid.,

p.

2044;

(d)

D.

F.

Shriver

and

J.

Power,

J.

Amer.

Chem.

SOC.,

1966,

88,

1672.

67

A.

Finch, P.

J.

Gardner,

and

K.

K.

Sen

Gupta,

J.

Chem.

SOC.

(A),

1966,

1367.

68

(a)

G.

Kodama

and

H.

Kondo,

J.

Amer.

Chewa.

Soc.,

1966,

88,

2045;

(b)

A.

R.

Gatti and

T.

Wartik,

Irtorg.

Chem.,

1966,

5,

329, 2075.

6B

J.

R.

Weaver and

R.

W. Parry,

Inorg.

Chem.,

1966,

5,

713,

718.

7O

(a)

P. Powell

and

H.

Nath,

Chem.

Comm.,

1966,637;

(b)

M.

P.

Johnson and

D.

F.

Shiver,

J.

Amer. Chem.

SOC.,

1966,88,

301;

(c)

M.

P.

Johnson,

D.

F.

Shiver,

and

S.

A.

Shiver,

&bid.,

p.

1588.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

DOWNS,

EBSWORl'H AND TURNER:

THE

TYPICAL

ELEMENTS

145

1lB

magnetic resonances

of

new compounds suggest substantial back-

donation

of

metald-electrons to the boron. Analogous compounds

of

cobalt and

platinum,

viz.,

(Ph,PCH,CH,PPh,), Co(BPh,), and (Et,P),Pt(BPh,)Cl, have

been ~repared.71~ Metal atoms have also been incorporated into delocalised

bonding

units. Thus, metallation

of

decaborane

is

believed to give solvated

complexes wherein the metal atom

(Al,

Zn, or

Cd)

bridges the 6,9 positions

of

decaborane.72

Two

carborane derivatives in which

a

metal atom occupies

the twelfth icosahedral position

in

the otherwise open face

of

the C,B,Hll2-

(or

related) anion have been structurally characterised

by

X-ray methods

;

the proposed structure

of

the [C,BsH,,Re(CO),]- ion has thus been con-

hrmed,73Q whilst

a

new palladium compound

730

containing a tetraphenyl-

cyclobutadiene ring and the [B&,C2Me212- ion has

a

similar structure

(5).

Ph

Ph

(5)

[Reproduced

from

P.

A.

Wegner and

M.

F.

Hawthorne,

Chem.

Comm.,

1966, 861.1

General reviews about

B,-B,

boron hydride~,~*~ carboranes,

7Pb*

and

organo-substituted boranes

74b

have appeared. The theoretical aspects

of

bonding

in

boron hydrides continue to attract attention

:

Slater-type atomic

'l

(u)

H.

Noth and

G.

Schmid,

2.

anorg.

Chem.,

1966,

345,

69;

J.

Organometallic

Ohm.,

1966, 5, 109;

(b)

G.

Schmid and

H.

Noth,

2.

Naturforsch.,

1965,

20b,

1008.

78

N.

N.

Greenwood and

J.

A.

McGinnety,

J.

Chem.

SOC.

(A),

1966, 1090;

N.

N.

Greenwood

and

N.

F.

Travers,

Imrg.

Nuclear Chern. Letters,

1966,

2,

169.

7s

(a)

A.

Zalkin,

T.

E.

Hopkins, and

D.

H.

Templeton,

Inorg.

Chem.,

1966,

5,

1189;

Ann.

Reports,

1965,

62,

139;

(b)

P.

A.

Wegner and

M.

F.

Hawthorne,

Chem.

Cmm.,

1966, 861.

74

(a)

B.

M.

Mikhailov

and

M.

E.

Kuimova,

Rms.

Chem.

Rev.,

1966,35, 569;

(b)

T.

Onak,

Adv.

Orgunometallic Chem.,

1965,3,263

;

(c)

K.

Issleib,

R.

Lindner, and

A.

Tzschach,

2.

Chem.,

1966,

8,

1.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

146

INORGANIC

CHEMISTRY

basis functions have been used

vSu

to examine molecular charge distributions,

overlap populations, and other properties

of

some boron hydrides; for the

general three-centre two-electron system ZHZ, the energy, ZHZ bond angle,

and effective nuclear charge

of

Z are closely interrelated;75b application

of

LC(Hartree-Fock)AO molecular orbital theory to the

c2H6

and BaHs mole-

cules indicates

75c

that the different geometries hinge upon the contributions

of

the heavy atom p-functions

to

molecular bonding. Mass-spectrometric

procedures have been devised to identify labile borane specie~.~6~ Hence, the

pyrolysis of tetraborane(

10)

has been shown

76b

to produce

B,H,

as well as

di-,

penta-, hexa-, hepta-, octa-, and deca-boranes, and possibly nonaborane.

Monomeric BH, has been clearly identified

76c

in the pyrolysis of diborane,

as

have the new molecular species H,&@, and H4B607 (probably boroxine deri-

vatives) in the high-temperature reaction

of

boron with water vapour.76d

Similarly, the anions

BH4-,

B2H,-, B2H8-, B3H8-, B3H7-, B,H,-, B,H,-,

and

B5H1,-

(all with lifetimes

>

10-5

see.) have been identified

7Oe

when

B2H6

is

bombarded by krypton ions.

The BH, groups

of

zirconium and hafnium borohydrides

77a

are bonded

to the metal by hydrogen bridges, though a rapid exchange process renders

.

the bridge and terminal hydrogens magnetically equivalent

;

the

boro-

hydrides

of

zirconium and hafnium (but not of titanium and copper)

react with donor molecules

77b

to give metal hydride derivatives

[e.g.,

(n-C5H,),Zr(H)BH4]. The reaction of

bis(triphenylphosphine)copper(I)

borohydride with strong acids

78

gives salts containing the binuclear cation

[L2CuBH4CuL2]+ (L

=

PPh,),

the i.r. spectrum and reactions

of

which

suggest the structure

(6).

C1MgBH4,2THF (TI33

=

tetrahydrofuran)

is

dimeric in benzene solution with

a

dipole moment

of

6~,

but monomeric

in tetrahydrof~ran.7~ Octahydrotriborates,

e.g.,

Mg(B,H&,(THF), and

Mg(BH4)(B,H,),5THF, have been prepared by heating B2H6 with the

76

(a)

I?.

P. Boer,

M.

D.

Newton, and

W.

N. Lipscomb,

J.

Amer.

Chm.

SOC.,

1966,

88,

2361;

W.

E.

Palke and

W.

N. Lipscomb,

ibid.,

p.

2384;

(b)

K.

E.

Banyard and

N.

Shull,

J.

Chem. Phys.,

1966,

44,

384;

(c)

R.

J. Buenker,

S.

D.

Peyerimhoff,

L.

C.

Allen,

and J.

L.

Whitten,

ibid.,

1966,

45,

2835.

713

(a)

A.

D.

Norman,

It.

Schaeffer,

A.

B.

Baylis,

G.

A.

Pressley, jun., and

F.

E.

Stafford,

J.

Amer.

Chem.

SOC.,

1966,

88,

2151;

(b)

A. B. Baylis,

G.

A.

Pressley,

jun.,

M.

E.

Gordon, and

F. E.

Stafford,

ibid.,

p.

929;

(c)

A.

B.

Baylis,

G.

A.

Pressley,

jun.,

and

F. E.

Stafford,

ibid.,

p.

2428;

(d)

S.

K.

Gupta and

R.

F.

Porter,

J.

Phys.

Chem.,

1966,

70,

871;

(e)

Gr.

Hortig,

0.

Midler,

K.

R.

Schubert, and

E.

Fluck,

2.

Naturforsch.,

1966,

21b,

609.

77

(u)

B.

D.

James,

R.

K.

Nanda, and

M.

G.

H.

Wallbridge,

J.

Chem.

SOC.

(A),

1966, 182;

(b)

B.

D.

James,

R.

K.

Nanda, and

M.

G.

H.

Wallbridge,

Chm.

Comm.,

1966, 849.

78

I?.

Cariati and

L.

Naldini,

J.

Inorg.

Nuclear

Chem.,

1966,

28,

2243.

79

W.

E.

Becker and

E.

C.

Ashby,

Inorg.

Chena.,

1965,

4,

1816.

80

S.

He3mAnek and J. Plegek,

CoZZ.

Czech.

Cham.

Comm.,

1966,31, 177.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

DOWNS,

EBSWORTH

AND

TURNER:

THE

TYPICAL ELEMENTS

147

appropriate tetrahydroborate in ether solution. Sodium borohydride reacts

with aziridine in moist tetrahydrofuran,gl giving, probably, 1,2-azaboretidine

(7).

Spectroscopic evidence

82

suggests the formation of the HSBH,- anion

and probably (HS),BH,-

in

the thiohydrolysis of LiBH, in tetrahydrofuran

solutions at -22-0"; warming the solution to

30"

probably produces poly-

mers of the species SBH,-.

In the substituted monoborane HB( OCD,), the

B-H

bond length is curiously long

(1.24

A),S3

being almost identical with

that for BH,-. Properties of lithiomethyldimethylamine( dimethylamino-

methyl)dihydroborane,84 isolated from the reaction of butyl-lithium with

[H2B(NMe,),]C1, favour the cyclic structure

(8a.)

;

hydrolysis or reaction with

methyl iodide convert the compound into the new borane cations (8b)

or

(8c),

respectively. In the novel amine Me,N*BH,*CH,-NMe, the BH2 group

enhances the basicity

of

the amine,84 the borane adduct

of

which,

Me,N*BH,*CH,*NMe,,BH,, sublimes unchanged

in

vacuo

at

100".

Independent investigations

7GC9

85

suggest that the enthalpy for the pro-

cess B,H,(g)

+

2BH,(g) is

35

kcal./mole. Hydrogen-evolution measure-

ments during the hydrolysis of B,H, and BH,- are concordant

s

with the

formation

of

the intermediates BH,+aq.,

BH(

OH),,

or

BH(

OH),- according

H,B-CH,.NMe, H,B*CH,.NHMe,+ H,B*CH,*NMe,+

!-1

I

1

to whether the medium

is

acid, neutral,

or

alkaline, respectively.

1lB

n.m.r.

spectra support

8Ya

the formation of singly hydrogen-bridged amine-boranes

H,B-H-BH,-NH,Me,-,

(n

=

0,

2, or

3)

€Tom B,H, and the appropriate

amine at

-78";

with

1

mol. of amine the amine-boranes give the unsym-

metrical cleavage products [BH2(NH,Me,-,J2][BH4]. The structure

[Me2B(NH3)2]+[H,Bhle,]-

is

proposed

87b

for

the product of the direct reac-

tion of ammonia and tetramethyldiborane, whereas in ethereal solution the

non-electrolyte Me,BH,NR, is formed.

For

the dimethylammoniate

of

diborane the formulation [H,B(NH,Me),] +[BHa]

-

is

favoured.ss

With allene

B2H6 undergoes terminal addition

g9

producing

1

,%trimethylenediborane

(9),

noteworthy

for

its reversible polperisation.

Reaction of acetylene and B2H6 in an electric discharge

90a

yields, as the

major volatile products, the carboranes 1,6-C,B,H5,

1

,6-C,B4H6, 2,4-C2B,H,,

81

S.

Akerfeldt and

M.

Hellstrom,

Acta.

Chem.

Scand.,

1966,

20,

1418.

82

B.

F.

Spielvogel and

E.

F.

Rothgery,

Chem.

Comm.,

1966, 765.

T.

C.

Farrar,

J.

Cooper, and

T.

D.

Coyle,

Chem.

Conam.,

1966, 610.

N.

E.

Miller,

J.

Amer. Chem.

Xoc.,

1966,

88,

4284.

85

J.

Grotewold,

E.

A.

Lissi,

and

A.

E.

Villa,

J.

Chem.

SOC.

(A),

1966, 1038;

A.

B.

Burg

and Y.-C.

Fu,

J.

Amer. Chem.

SOC.,

1966,

88,

1147.

86

W.

L.

Jolly

and

T.

Schmitt,

J.

Amer. Chem.

Xoc.,

1966,

88,

4282.

(a)

S.

G.

Shore

and

C.

L.

Hall,

J.

Amer. Chem. SOC.,

1966,

88,

5346;

(b)

P.

C.

Moews,

jun.,

and R.

W.

Parry, Inorg. Chem.,

1966,

5,

1552.

0.

T.

Beachley,

Inorg. Chein.,

1965,

4,

1823.

H.

H. Lindner

and

T.

Onak,

J.

Amer.

Clwm.

SOC.,

1966,

88,

1886.

(a)

R.

N.

Grimes,

J.

Amer. Chem.

Xoc.,

1966,

88,

1895;

(b)

R.

N.

Grimes,

ibid.,

p.

1070;

(c)

R.

Koster,

H.-J. Horstschiifer,

and

P.

Binger,

Angew.

Chwn.,

Internat.

Edn.,

1966,

5,

730.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

148

INORGANIC

CHEMISTBY

B-methylated derivatives

of

these, and C,3-Me,-1,2-C2B,H3 [see

(lo)],

the last

of which represents

a

new isomer of the C2B3H5 system with one equatorial

and one apical carbon atom in the trigonal-bipyramidal framework.90b

Hydroboration of alkynylboranes by alkyldiboranes also affords substituted

C2B3 carb0ranes.m The base-catalysed rearrangement of 1,2- to

2,3-

dimethylpentaborane(9)

(1

1)

has been estab1i~hed;~l there are

signs

of

weakening

of

the B-B bond of the basal Me-B-B-Me unit relative

to

H-B-B-H. The AlC1,-catalysed chlorination of pentaborane(

9)

probably

involves electrophilic attack

of

the borane cage by C1+ (giving l-chloro-

pentaborane), whereas the uncatalysed reaction proceeds through radical

formation (giving mainly 2-~hloropentaborane).~2 Mono-,

Q3a9

di-,Q" tri-,9"

and tetracarbahexaboranes

sge

have now been characterised.

The

respective

parent compounds 2-CB,Hg, 2,3-C,B,H8, 2,3,4-C3B,H,, and 2,3,4,5-C4B,H,

are structurally related to the B,H,, molecule by successive substitution

of

CH

for isoelectronic BH, groups

in

the basal plane (12). With NaH

in

diglyme, 2,3-C2B4Hs suffers reversible loss of one

of

the bridge hydrogens

to

form the 2,3-C,B4H,-

Alk

ylated

2,4-dicarbaclovoheptaboranes(7)

are produced together with monocarbahexaboranes(9) by the dehalogenation

of

organofluoroboranes.93b Mass-spectrometric techniques

g4

permit the

identification of the boranes

BsH12

and

B9Hl,

originating from the reaction

between liquid B,Hll and gaseous

;

earlier reports

of

heptaboranes are

questioned. With the synthesis of B7C,Hg and two isomeric BsC2H1,

systems, and an improved route to BsCzHs carb~ranes,~~ the series

B,C,H,+,

has been completed from

n

=

3

to

10; tentative structural assignments are

given (13). The thermal isomerisation

of

B,HsC,Me2 at

m.

350"

is clearly

reminiscent of the behaviour

of

icosahedral carboranesmg5 Oxidation of the

corresponding B,C2H11 carborane gives dicarbanonaboranes(

13),

B7C2H1,RR'

(R,R

=

H,

Me,

or

Ph)

96

for

which

the

structure

(14)

is

proposed. With

aqueous alkali B7C,Hl,Me, forms B7C,H,,Me2-, whilst pyrolysis

of

the dicar-

banonaboranes produces BnC2Hn+2 carboranes. Salts of

two

novel

poly-

hedral borane anions BQHg2- and

BllHl12-,

from the thermal decomposition

of the corresponding salts

of

the

B3H,-

and B11H132- ions, respectively, me

thermally, though not hydrolytically, In solution the BQHQ2- ion

appears

to

have

a

tricapped trigonal-prismatic structure [see

(13)].

Decaborane( 14) does not

fit

well

into

a thermochemicctl bond-energy

scheme with the lower b~ranes.~g Noteworthy developments

in

decaborane

91

T.

Onak,

L.

B.

Friedman,

J.

A.

Hartsuck, and W.

N.

Lipscomb,

J.

Amer.

Chm.

SOC.,

1966, 88,3439;

L.

B.

Friedman and

W.

N.

Lipscomb,

Inorg.

Chern.,

1966,

5,

1752.

92

D.

F.

Gaines,

J.

Amr.

Chem.

SOC.,

1966,

88,

4528.

s3

(a)

T.

P.

Onak,

0.

B.

Dunks,

J.

R.

Spielman, F.

J.

Gerhart, and

R.

E.

Williams,

J.

Amer. Chem.

Xoc.,

1966,88,2061;

(6)

R.

Koster

and

M.

A.

Grassberger,

Amgew.

Chem.,

Internat.

Edn.,

1966,

5,

580;

(c)

T.

Onak

and

G.

B.

Dunks,

Inorg.

Chem.,

1966,

6,

439;

(d)

C.

L.

Bramlett and

R.

N.

Grimes,

J.

Amer.

Chern.

SOC.,

1966,88,4269;

(e)

P.

Binger,

Tetrahedron Letters,

1966, 2675.

04

J.

F.

Ditter,

J.

R.

Spielman, and

R.

E.

Williams,

Inorg.

Chem.,

1966,

5,

118.

95

F.

N.

Tebbe,

P.

M.

Garrett,

D.

C.

Young,

and

M.

F.

Hawthorne,

J.

Amer.

Ch.

96

F.

N.

Tebbe,

P.

M.

Garrett, and

M.

F.

Hawthorne,

J.

Arner.

Chern.

Soc.,

1966,

97

F.

Klanberg and

E.

L.

Muetterties,

Inorg.

Chem.,

1966,

5,

1955.

g8

S.

R.

Gunn and

J.

H.

Kindsvater,

J.

Phys.

Chem.,

1966,70,1114.

SOC.,

1966,

88,

609.

88,

607.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

DOWNS,

EBSWORTH

AND TURNER:

THE

TYPICAL

ELEMENTS

149

I

Arc

hi

medean

B7C2H9

Tr

i

capped

anti prism

trigonal prism

(13)

B

i

capped Arch imedean

antipr ism

0.

Possible positions

for

C

atoms

chemistry include the metallation reactions,72 identification of two isomeric

B10H13NH3- ions distinguishable by their susceptibility to nucleophilic

characterisation

100

of

the salt Na2B,,Hlz, and n.m.r. evidence

lol

that the adduct BloH1,,2DMF

(DMI?

=

dimethylformamide) contains

the units B-0-CH=NMe,. Diazonium derivatives formulated

as

l,lO-+N,Blo~-X,N,+

(X

=

H,

C1,

or

I)

undergo nucleophilic replacement

reactions and are thus useful synthetic intermediates ;lo2 substitution

of

CN-,

N3-, or

OCN-

for halogen in polyhalogenated

BloHl02-

and

B12H122-

deri-

vatives can also be effected by photolysis.lO3

The

oxidation

of

polyhedral

boranes produces free radica1~,~04 which, according to kinetic measurements,

constitute the &st step in the oxidative coupling of Bl0H,,Z- ions giving

Bzo

species

;

since the radicals produced from

B1,HlO2-

and

B,,H1,0H4-

appear

similar, boron cages joined by

a

B-B

bond probably remain electronically

isolated. The new undecaborane BllH15, prepared in solvated form by

acidification

of

NaBl1H1,

in

non-aqueous solution,l05 reacts with water,

alcohol, or organic sulphides, producing a second new, solvated undecaborane

B,lHl,. For the unusual

1

:

1

adducts of decaborane(l4) with alkyl isocya-

nides, the zwitterionic structure R+NR2-[CBloHl2-]

is

suggested, the carbon

atom forming part

of

the open face of an ll-particle icosahedral fragment.lo6

A

similar unit is found in the C,B,H,l-metal derivatives and, according

to

spectroscopic evidence, in the dicarbaundecaborate anions

R'R''C,B,H,X-

(R

=

H,

Me,

or

Ph;

X

=

Br

or

I)

where the substituents

R',

R",

and

X

are

Og

E.

L.

Muetterties and

F.

Klanberg,

Imrg.

Chem.,

1966,

5,

315.

loo

P.

H.

Wilks

and

J.

C.

Carter,

J.

Amer. Chem.

SOC.,

1966,

88,

3441.

Iol

W.

R.

Hertler and

E.

L.

Muetterties,

Inorg.

Chem.,

1966, 5, 160.

lo2

W.

H. Knoth,

J.

Amr.

Chent.

Soc.,

1966,

88,

935.

lo3

S.

Trohenko,

J.

Amer.

Chem.

Soc.,

1966,

88,

1899.

Io4

J.

S.

Lewis and

A.

Kaczmarczyk,

J.

Amer.

Chm.

Soc.,

1966,

88,

1068;

R. L.

Io5

L.

J.

Edwards and

J.

M.

Makhlouf,

J.

Amer.

Chm.

SOC.,

1966,

88,

4728.

Io6

D.

E.

Hyatt,

D.

A.

Owen, and

L.

J.

Todd,

Irwrg.

Chena.,

1966, 5, 1749.

Middaugh and F. Farha,

jun.,

ibid.,

p.

4147.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

150

INORUANIC

CHEMISTRY

attached, respectively, to adjacent

C, C,

and

B

atoms of the open face.lO7a In

the neutral dicarbaundecaboranes(

13)

R'R"C2BgHloX, two protons appear

to be weakly bound to boron atoms in the open face;1°7a species of this type,

viz.

,

X2C2BgHIl, are also formed

by alcoholic cleavage of CC'-dihalogeno-

carboranes, l,2-~C,B1,Hl,. Since,

in

the reaction

of

piperidine with mono-

and di-C-substituted derivatives of

1

,2-C2B10H12,

asymmetrically substituted

carboranes give only one correspondingly substituted C,BgH12- anion,l08

boron-elimination probably occurs at the

3,6

positions of the

C,Bl0

cage

where the electron density is lowest. The skeleton of the dicarbaunde-

caborane(

1

l),

Me2C2BsHg, consists

of

a boron-bridged BloH1,-like framework

with carbon atoms in the

6,9

po~itions;~OS the B11H112- ion should be struc-

turally analog0us.~7

(-H7H/-H

BT

HB

H,

R'

The positions of electrophilic

'H

\

R'

(14)

CI,

,CI

\/

Pd

Ph2P

bromination

of

1,2-dicarbaclovododeca-

borane( 12) and its 1,2-dimethyl derivative have been established by crystal-

lographic studies

of

the products;59,

l10

the order

of

substitution is B-9,12 and

then

B-8,10,

the

four

most electron-rich sites according to molecular orbital

calculations. This order

is

supported by the fact that electrophilic halo-

genation of a

1

-organo- 1,2-carborane gives two monohalogenocarboranes but

only one

dihalogenocarborane,llla

and by the synthesis (from appropriate

halogenodecaboranes and acetylenes)

of

carboranes containing halogen

atoms

in

specific 1ocations.lllb There is evidence

of

increased electron

density in the carborane nucleus of

1

,2-Me2C2BloHlo compared with

1

,2-H2C2B10H10, though contrary

to

some reports,l10 tetrabromo-derivatives

of

both have in fact been obtained.lllc

1,7-Dicarbaclovododecaboranes

(m-

carboranes) can be similarly halogenated, the sites

of

attack being initially

B-9,10

(on the strength

of

electron densities and number of isomers ob-

tained).llld

The mechanism

of

the thermal isomerisation

of

icosahedral car-

boranes (and similar rearrangements)

has

been discussed.

l2a

Bulky

R,Si

substituents attached to the carbon atoms of the o-carborane cage facilitate

isomerisation, suggesting that steric factors are important,112b and activation

lo7

(a)

F.

P.

Olsen and

M.

F.

Hawthorne,

Inorg.

Chem.,

1965,

4,

1839;

(6)

L.

I.

Zakharkin

and

L.

S.

Podvisotskaya,

Bull.

Ad.

Sci.

U.S.S.R.,

1966,

742.

108

L.

I.

Zakharkin and

V.

N.

Kalinin,

Doklady

Chem.,

1965,

163,

631.

loa

C.-c.

Tsai and

W.

E.

Streib,

J.

Amer.

Chem. Xoc.,

1966,

88,

4513.

110

J.

A.

Potenza and

W.

N.

Lipscomb,

Inorg.

Cherrz.,

1966,

5,

1471, 1478, 1483.

111

(a)

L.

I.

Zakharkin

and

V.

N.

Kalinin,

Bull.

Acad. Sci. U.X.X.R.,

1965, 1287;

(b)

L.

I.

Zakharkin

and

V.

N.

Kalinin,

ibid.,

1966, 566;

(c)

Idem,

ibid.,

p.

549;

(d)

L.

I.

Zakharkin and

V.

N.

Kalinin,

Doklady

Akad.

Nauk.

S.X.S.R.,

1966,

169,

590.

112

(a)

W.

N.

Lipscomb,

Science,

1966,

153,

373;

(b)

R.

M.

Salinger

and

C.

L.

Frye,

Imrg.

Chem.,

1965,

4,

1815.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

DOWNS,

EBSWORTH

AND

TURNER:

THE

TYPICAL

ELEMENTS

151

enthalpies imply that some skeletal deformation required in the transition

state is already present

in

the ground sta,te of the substituted carboranes.

With the synthesis

of

C-carboranyl alkanes,113a cycloalkane deri~atives,ll~~

carboxylic acids,

l1

*

alcohols,

3d

amines,

11%

halides,llgf ketones,ll3g and

substituted phenyl derivatives,113h an extensive organic chemistry

of

car-

boranes

is

taking shape. The range of boron-substituents is more limited,

but, apart from B-halogeno-compounds,

B-monohydroxy-derivatives

have

also been synthesised.ll* The electron-attracting propensity

of

the carborane

nucleus is evident from the acidity of

1

,2-bis(hydroxymethyl)-o-carborane,

and the weak basicity

of

the

1

,2-bis(aminomethyl)-compound,113i

the

decarboxylation

of

carboranylcarboxylic acids by metal acetylacetonates,

11*

the

''

positive

"

character of the halogen in

C-halogeno~arboranes,l~~f

and

the influence of the carboranyl group

on

aromatic substitution reactions

of

pheny1~arboranes.l~~~ Numerous facts,

e.g.,

the relative dissociation con-

stants of corresponding carboxylic acids,ll& suggest that the order of

acceptor power is

:

o-carborane>m-carborane.

The coloured paramagnetic

solutions formed from aryl-substituted 1,2-carboranes and potassium

in

an

ether solvent presumably contain anion free-radicals, the electron spin

resonance spectra of which suggest

a

highly

delocalised unpaircd electron,l15

whereas the diamagnetic solution formed from vinylcarborane is believed

to

contain

a

dimeric dianion. Bis-1,2-carborane is composed of two

C2B,,

icosahedra joined by a

C-C

single bond.l16 Coupling reactions of m-carboranes

tendto givepolymerswith, for example, bridging carbonyl,113b di~rganotin,ll~~

chlor~phosphine,~~~~

or

siloxane

117c

groups. C-Substituted sulphurll8U and

phosphorus

llSb

derivatives

of

o-carboranes form metal chelate systems

[typically(

15)].

The remarkable resistance to electrophilic attack of

C-

carboranyl mercury compounds

is

attributed

l18C

to the combination of

unusual co-ordination of the carboranyl carbon atom, steric hindrance, and

acceptor properties of the carborane nucleus.

113

(a)

L.

I.

Zakharkin and

A.

V.

Kazantsev,

Bull.

Acad. Sci.

U.S.S.R.,

1965, 2153;

(b)

J.

P.

Reiner,

R.

P. Alexander, and

H.

Schroeder,

Inorg.

Chm.,

1966,

5,

1460;

L.

I.

Zakharkin,

Bull.

Acad.

Sci.

U.S.S.R..

1965, 1083;

(c)

L.

D.

Hansen,

J.

A. Partridge,

R.

M.

Izatt, and

J.

J.

Christensen,

Inorg.

Chem., 1966,

5,

569;

V.

I.

Stanko and

A.

I.

Klimova,

J.

Gen. Chern.

(U.S.S.R.),

1966,

36,

165;

N.

R.

Fetter,

Canad.

J.

Chm., 1966,

44,

1463;

(d)

L.

I.

Zakharkin and

A.

V.

Kazantsev,

Bull.

Acad.

Sci.

U.S.S.R.,

1966,

1128;

(e)

L.

I.

Zakharkin and

V.

N.

Kalinin,

J.

Gem.

Chem.

(U.S.S.R.),

1965, 35, 1878;

(f)

L.

I.

Zakharkin and L.

S.

Podvisotskaya,

Bull.

Ad.

Sci.

U.S.S.R., 1965, 1422;

(9)

L..I.

Zakharkin

and

A.

I.

L'vov,

ibid., 1966, 128;

(h)

L.

I.

Zakharkin and

V.

N.

Kah,

zbid.,

1965, 2173;

Dolcludy

Chem.,

1965,

164,

904;

(i)

T.

V.

Potapova,

R.

A.

Svitsyn,

A.

F.

Zhigach,

V.

T.

Laptev,

I.

V.

Persianova,

and

P.

Z.

Sorokin,

Buss.

J.

Inorg.

Chem.,

1965,

10,

1133.

114

L.

I.

Zakharkin,

V.

N.

Kalinin, and

L.

S.

Podvisotskaya,

Bull.

Acad.

Sci.

U.S.S.R.,

1965, 1684.

116

K.

A. Bilevich, L.

I.

Zakharkin, and

0.

Yu.

Okhlobystin,

Bull.

Acad. Sci.

U.S.S.R.,

1965, 1887.

llS

L.

H.

Hall,

A.

Perloff,

F.

A.

Mauer,

and

S.

Block,

J.

Chem. Phys.,

1965,43, 3911.

11'

(a)

S.

Bresadola,

F.

Rossetto, and

G.

Tagliavini,

Chem.

Cmm.,

1966, 623;

(b)

R.

I?.

Alexander and H. Schroeder,

Inorg.

Chem.,

1966, 5,493;

(c)

S.

Papetti,

B.

B. Schaeffer,

A.

P.

Gray, and

T.

L.

Heying,

J.

Polymer

Sci.,

Pt.

A-1,

1966,

4,

1623.

118 (a)

H.

D.

Smith,

jun.,

C.

0.

Obenland, and

S.

Papetti,

Inorg.

Chem.,

1966,

5,

1013;

(b)

L.

I.

Zakharkin and

G.

G. Zhigareva,

Bull.

Acad.

Sci.

U.S.S.R.,

1965, 905;

(c)

L.

I.

Zakharkin,

V.

I.

Bregadze, and

0.

Yu.

Okhlobystin,

J.

OrgawrnetaElic

Ohm.,

1966,

6,

228.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

152

INORGANIC

CHEMISTRY

U

[Reproduced

from

M.

F.

Hawthorne

and

R.

L.

Pilling,

J.

Amer.

Chem.

Soc.,1966,:88,

3873.1

(17

b)

The

BZOHIa2-

ion undergoes reversible isomerisati~n,~~~

to

give a

"

photo

"

ion

probably having the structure indicated

(16).

Another remarkable

polyborane, the adduct B2,H1,,3MeCN, contains the molecular unit

B20H,a(NCMe)2 with the structure (17a), whose formation involves rearrange-

ment of the

B,,

unit

of

B,H1,

(17b),

giving

a new framework composed

of

B1,

and

B,,

icosahedral units with

a

common triangular face.120

The synthesis of organohalogenoboranes has been reviewed,lzl and

differences in disproportionation tendencies

of

alkylhalogenoboranes,122

apparently due to thermodynamic factors, have been discussed. The difunc-

tional Lewis acid

1,Z-bis(difluorobory1)ethane

forms adducts

of

the type

C2H4(BF2),,2D

(D

=

Me,O

or

THF),123 but with (Ph&O or MeOCPh,,

1

:

1

complexes also result, probably with the structure (18). Infrared spectra

of

BE',

trapped

in

low-temperature matrices support earlier evidence

of

llD

M.

F.

Hawthorne

and

R.

L.

Pilling,

J.

Amer.

Chem.

Soc., 1966,

88,

3873.

120

J.

H.

Enernark,

L.

B.

Friedman,

and

W.

N. Lipscomb,

Inorg.

Chem.,

1966,

5,

121

K.

Niedenzu,

Organometallk

Chm.

Rev.,

1966,

1,

305.

122

P.

A.

McCusker and

J.

H.

Bright,

J.

Inorg.

Nuclear

Chem.,

1966,

28,

2261

18s

M.

J.

Biallas and

D.

F.

Shiver,

J.

Amer.

Chem.

SOC.,

1966,

88,

375.

2168.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

DOWNS,

EBSWORTH

AND

'TURNER:

THE

TYPICAL

ELEMENTS

153

association,12* being compatible with the formation of

a

bridged her

species. Evidence is also presented

125

supporting the formation of the

B,F,-

ion

in

the reaction

of

amine tetrafluoroborates

with

BF,.

To

clarify

the status

of

certain fluoroborates, the interrelationship

of

the four primary

compounds

BF,,

B,O,,

HI?,

and

H20

has been expressed

in

the form of

a

"

genealogical tree."

126

Solvent- and concentration-dependent

llB

and

19F

n.m.r. parameters of the

BF4-

ion have been related to solvation

effects.127 The redistribution behaviour

of

boron halides and properties

of

the mixed halides have been correlated

128

with

n-bonding effects.

n-Bonding in aminoboranes has been the subject

of

molecular orbital cal-

culations, and mass-spectrometric measurements.129aP

b

Analysis

of

the

vibrational spectra

of

l0B-substituted dialkylaminoboranes, confirming the

interaction

of

B-N

and

GN

stretching vibrations,

1m

shows that infrared

frequency shifts attributed to

B-N

motions are not reliable indices of

z-

bonding; the same cautionary note applies to borazine systems.l3Qb

The

factors controlling the polymerisation of aminoboranes have been elabor-

ated.

lS1

Novel aminoboranes include various N-silyl deri~atives.13~a~

b

Di-

p-tolylcarbodi-imide reacts with

B-X

groups

(X

=

C1,

Br,

Ph, OMe,

NEt,,

or

SBun)

by insertion, to give substituted aminoboranes,

e.g.,

Y,B*NTol*C( :NTol)*X, whence the relative migratory aptitudes

of

different

groups has been deduced.

lS3

Dehydrohalogenation of amine-boranes affords

a

useful route to amin~boranes,~~~~ but only bulky amines like Et,N effect

this change

134

in C1,B,NHMe2; other amines yield, under similar conditions,

bis-amine complexes formulated as [Amine(Me,hTH)BCl,]Cl. Properties

of

the aminoboranes include the formation of charge-transfer complexes with

iodine,

35a

thermal elimination reactions giving cyclic

B-N

compounds,1S2b

lZ4

J.

M.

Bassler,

P.

L.

Timms,

and

J.

L.

Margrave,

J.

Chem. Phys.,

1966,

45,

2704;

lZ5

J.

J.

Harris,

Inorg. Chem.,

1966,

5,

1627.

lZ6

S.

Pawlenko,

2.

unorg. Chem.,

1966,

547,

1,

7.

lZ7

R. Haque and

L.

W. Reeves,

J.

Phys.

Ciaem.,

1966,

70,

2753;

R.

J.

Gillespie

and J.

S.

Hartman,

J.

Chem. Phys.,

1966,

45,

2712.

M.

F.

Lappert,

J.

B. Pedley, P.

N.

K.

Riley,

and

A.

Tweedale,

Chern.

Comm.,

1966, 788.

12*

(a)

P.

G. Perlks and

D.

H.

Wall,

J.

Chem.

SOC.

(A),

1966, 1207;

(b)

J.

C.

Baldwin,

M.

F.

Lappert,

J.

B.

Pedley,

P.

N.

K.

Riley, and

R.

D.

Sedgwick,

Inorg. Nuclear Chem.

Letters,

1965,

1,

57.

130

(a)

H.

J.

Becher and

H.

T.

Baechle,

2.

ghys.

Chem.

(Frankfurt),

1966,

48,

359;

(b)

R.

E. Hester and

C.

W.

J. Scaife,

Spectrochim. Acta,

1966,

22,

455,

755.

131

M.

F.

Lappert,

M.

K.

Majumdar, and B.

P.

Tilley,

J.

Chern.

SOC.

(A),

1966, 1590.

132

(a)

R.

L. Wells and

A.

L.

Collins, Inorg.

Chem.,

1966,

5,

1327;

(b)

P.

Ceymayer

and

E.

G. Rochow,

Monatsh.,

1966,

97,

429, 437.

133

R. Jefferson,

M.

F.

Lappert,

B.

Prokai, and B. P. Tilley,

J.

Chem.

SOC.

(A),

1966, 1584.

134

H.

Noth,

P.

Schweizer, and

F.

Ziegelgansberger,

Chena.

Ber.,

1966,

99,

1089.

135

(a)

I.

D.

Eubanks and J.

J.

Lagowski,

J.

Amer. Chem.

SOC.,

1966,

88,

2425;

cf.

R.

G. Steinhardt,

jun.,

G.

E. S.

Fetsch and

M.

W. Jordan,

ibid.,

1965,

43,

4528.

(b)

N.

N.

Greenwood and

J.

Walker,

Inorg. Nuclear Chem.

Letters,

1965,

1,

65.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

154

INORGANIC CHEMISTRY

and redistribution rea~tions,~~5~ n.m.r. studies

of

which indicate the sequence

MezNBX2

<

Et,NBX,

<

BX,

<

PhBX, for the relative rates of halide

exchange. Monomeric boron imides, C,FE',B:NAr

(Ar

=

p-T/leO*C,H,

or

mesityl), are produced

136

[with small amounts

of

the dimer

(C,F,B*NAr)g

when

Ar

=

p-MeO*C,H4] from C,F,BCl, and

ArNH,.

Dimethylboron

azide

13'

associates reversibly

in

the liquid phase and forms

1

:

1

complexes

with bases like pyridine.

Apart from proton n.rn.r. surveys

138

and vibrational analyses,13*b most

of the advances in borazine chemistry have been associated with preparative

reactions

;139a

among the new borazines synthesized are fluoro-aryl and -alkyl

derivatives,139b Linear polyborazines (formed

by

condensation reactions

of

simple borazines with diamines) ,lZgc and hydrolytically stable derivatives

with bulky B-substit~ents.~~~~

The reaction of B-trichloroborazine with

MeMgBr is reported to give

a

polycyclic B-methylborazine, but whether

this

has

a

naphthalene- or biphenyl-like structure

has

yet to be re~olved.139~

More

derivatives

of

the cyclotetrazenoborane system have been charac-

terised, thus confirming the generality of the preparative reaction between

primary amine-boranes and organic azides.140 Compounds containing boron

bonded to the nitrogen of a pyrazole nucleus

l4l

may take the form

of

B-N

heterocycles and metal chelates.

Cyclic species

of

composition (BH2NH2),

(n

=

2,

3,

5,

and possibly

4),

resulting from the reaction

of

NaNH,

with

[H2B(NH3),]BH, in liquid ammonia, have also been described,l42 as have

members of

a

new class of heterocycles containing the elements boron, nitrogen,

and phosphorus in the same ring.143

The preparation of numerous hetero-

cycles containing carbon as well

as

boron and nitrogen has been rep~rted,l~*~

for example, by the reaction

of

am-diamines with amin0boranes.l4*~

The

dimethylaminomethylborane

cyclic dirner, [H,B*CH,*NMe,],,

is

relatively

stable with respect to thermal dissociation, unlike the analogous amino-

methyl(dimethy1)borane

;145

this

is

in

line with simple

Lewis

acid-base

affinities.

Some characteristic features of the crystal chemistry of borates hare been

outlined,146 and

a

review of organosulphur-boron compounds

l47

has

136

P.

I.

Paet,zold and

W.

M.

Sirnson,

Angew. Chem., Internat.

Edn.,

1966,

5,

842.

13*

A.

Grace and

P.

Powell,

J.

Chem.

SOC.

(A),

1966, 1468.

P.

I.

Paetzold and

H.

J.

Hansen,

2.

anorg. Chem.,

1966,

345,

79.

(a)

E.g.,

A.

Grace and P. Powell,

J.

Chem.

SOC.

(A),

1966, 673;

(b)

A.

MelIer,

M.

Wechsberg,

and

V.

Gutmann,

Monatsh.,

1966,97,619,1163;

(c)

J.

M.

Turner,

J.

Chem.

SOC.

(A),

1966,401,410,415;

(d)

K.

Nagasawa,

Inorg.

Chem.,

1966,5,442;

(e)

J.

L. Boone

and

G.

W. Willcockson,

ibid.,

p.

311;

A.

Meller

and

H.

Egger,

Monatsh.,

1966,

97,

790.

140

J.

H.

Morris

and

P.

G.

Perkins,

J.

Chem.

Soc.

(A),

1966, 576,

580;

A.

J.

Downs

and

J.

H.

Morris,

Spectrochim. Acta,

1966,

22,

957;

cf.

Ann.

Reports,

1965,

62,

360.

141

S.

Trofimenko,

J.

Amer. Chem.

SOC.,

1966,

88,

1842.

K.

W.

Boddoker,

S.

G.

Shore,

and

R.

K.

Bunting,

J.

Amer.

Chem.

SOC.,

1966,

88,

4396.

143

F.

Gr.

Shorif and

C.

D.

Schmulbach,

Inorg.

Chem.,

1966, 5, 322.

144

(a)

G.

Hesse,

H.

Witte,

and

H.

Haussleiter,

Angew. Chem., Internat.

Edn.,

1966,

5,

723;

G.

Hesse,

H.

Witte, and

W.

Gulden,

Tetrahedron Letters,

1966, 2707;

(b)

W.

Weber,

J.

W.

Dawson, and

K.

Niedenzu,

Irwrg. Chem.,

1966,

5,

726;

K.

Niedenzu and

W.

Weber,

2.

Naturforsch.,

1966,

21b,

811;

K.

Niedenzu and P. Fritz,

2.

anorg.

Chem.,

1965,340, 329.

146

N.

E.

Miller,

M.

D.

Murphy,

and

D.

L.

Reznicek,

Inorg. Chem.,

1966,

5,

1832.

1413

V.

B.

Kravchenko,

J.

Strwt.

Chem.,

1965,

6,

76.

R.

H.

Cragg and

M.

F.

Lappert,

Organometallic Chem.

Rev.,

1966,

1,

43.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

DOWNS, EBSWORTH

AND

TURNER:

THE

TYPICAL

ELEMENTS

155

appeared. Convenient syntheses

of

boroxine

lPgU

and trimethylboroxine

14gb

are described. Boroxine reacts rapidly14& with CO

to

give BH,,CO.

H2B203

and &B@, have been identified

in

the gas-phase oxidation

of

B,Hlo,

B5H9,

and BH,,CO; the short-lived species

€330

or

H2BOH

and

H,B02 (borane peroxide) are likely intermediate~.l4~ Reports have appeared

of

new derivatives

of

ring

systems containing boron, carbon, and either

oxygen

or

sulphur,

e.g.,

1,3,2-dioxaborinan

150°

and 1,2-thiaboro1an;l50b the

acceptor behaviour

of

some

of

these systems has been investigated.*

4-

and

6-membered

B-S

ring compounds have been prepared

l5la

by the reaction

of

H2S

with trialkylamine-boranes

;

5-membered 1,3,44rithiadiborolan rings

result from the cleavage

of

polysulphur compounds

(H2S,,

S,,

disulphides) by

boron halides.151* Heating

of

2,5-di-iodo-l,3,4-trithiadiborolan

with

BI,

causes ring-expansion with the formation

of

2,4,6-tri-iodo-l,3,5-trithiatri-

borinan.151b 6-Membered B-P heterocyclic compounds substituted at

phosphorus have also been characterised.152

2,2'-Bipyridyl (bipy) forms para- and dia-magnetic chelate compounds

in

which boronis stabilised in unusual oxidation states,lL3

e.g.,

(Me,N)2B(bipy).

The status

of

boronium salts

is

ambiguous; although the absorption spectra

of

the diphenylboron and 9-borafluorene cations have been satisfactorily

interpreted,l540 and salts

of

the type @3un2B( amine),]+Cl- are reported,154*

attempts to characterise phenylboronium cations have been unsuc~essful.~~~

The CF, groups of the compounds CF3BBu2 and CF3BF2 suffer CF,-elimina-

tion

only

in the presence of catalysts;l55

in

vacuo

at room temperature the

compounds are said to be

"

stable

for

months." The extent

of

B-C n-bonding

in vinylboranes has been gauged from spectroscopic

156u

and molecular

orbital

166b

considerations. The relative reactivities of competing

B-X

sites

with respect to organometallic compounds have been compared.l57

Recent surveys concern general features

of

metal borides

1580

and the

structural properties

of

boron and borides containing polyhedral

B,,

units.15gb

14*

(a)

L.

Barton, F. A.

Grimm,

and R.

F.

Porter,

Inorg.

Chena.,

1966,

6,

2076;

(b)

M.

W.

Rathke and

H.

C.

Brown,

J.

Am.

Chem.

Soc.,

1966,

88,

2606;

(c)

S.

K.

Wason and R.

J.

Porter,

Inorg. Chem.,

1966,

5,

161.

loS

L.

Barton,

C.

Perrin,

and

R.

F. Porter,

Inorg.

Chm.,

1966,

5,

1446.

lSo

(a)

W.

G.

Woods

and P.

L.

Strong,

J.

Amer.

Chm.

SOC.,

1966,

88,

4667;

(b)

B.

M.

Mikhailov,

V.

A.

Dorokhov, and

N.

V.

Mostovoi,

Dokladp

Chem.,

1966,

166,

1114.

lS1

(a)

J.

A. Forstner and

E.

L.

Muetterties,

Inorg.

Chem.,

1966,5,164;

(b)

M.

Schmidt

and

W.

Siebert,

2.

anorg.

Chem.,

1966,

345,

87;

M.

Schmidt

and

W.

Siebert,

Angew.,

Chm.,

Internat.

Edn.,

1966,

5,

697.

lS2

R.

I.

Wagner and

C.

0.

Wilson,

jun.,

Inorg.

Chna., 1966,

5,

1009.

16s

M.

A.

Kuck

and

G.

Urry,

J. Amer.

Chem.

Soc.,

1966, 88,426.

154

(a)

D.

R.

Armstrong and P.

G.

Perkins,

J.

Chem.

SOC.

(A),

1966, 1026;

(b)

T.

A.

Shchegoleva and

33.

M.

Mikheilov,

Bull.

Acad.

Sci.

U.S.S.R.,

1965,693;

(c)

R.

B.

Moodie,

B.

Ellul, and T.

M.

Connor,

Chem.

and Ind.,

1966, 767.

lS6

T.

D.

Persons,

J.

M.

Self,

and L.

H.

Schaad,

AD

620328,

U.S.

Oovt.

Res. Develop.

Rept.,

1965,

40,

38

(Chem.

Abs.,

1966,

64,

6674e).

16e

(a) K.

Niedenzu,

J.

W.

Dawson,

G.

A.

Neece,

W.

Sawodny,

D.

R.

Squire,

and

W.

Weber,

Inorg.

Chtm.,

1966,5,2161;

K.

Niedenzu and

W.

Sawodny,

2.

anorg.

Ch.,

1966,

844,

179;

(b)

D.

R.

Armstrong and P.

G.

Perkins,

Thoretica

China.

Acta,

1966,

4,

69,

362.

1s7

M.

F.

Lappert and

M.

K.

Majumdar,

J.

Organometallic

Chn.,

1966,

6,

316.

lS*

(a)

R. Thompson,

"

Borides:

Their Chemistry and Applications,''

Roy.

Inst.

Chem.

Lecture

Ser.,

1966;

N.

N.

Greenwood,

R.

V.

Parish, and P.

Thornton,

Qwrt.

Rev.,

1966,

20,

441;

(b)

V.

I.

Matkovich, R. F. Giese,

jun.,

and

J.

Economy,

2.

Kht.,

P

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

156

INORGANIO

CHEMISTRY

B,,

icosahedra are the basic structural units of

AIBl,

(but not

AIB1,,

ap-

parently),15& whereas ScB12 and YB,, contain cubo-octahedral arrays of

boron atoms.158d

A

boride

of

potassium, KB,, has been prepared for the

first

time.

158e

Reviews of general interest have appeared on complex

alumino hydr ides,

59a

or

g

anoaluminium and aluminium-p hosp horus

161

compounds. Advances in aluminohydride chemistry have included the

synthesis of hexahydroaluminates

M,Al€&

(M

=

Li or Na) by two different

methods.159b The i.r. spectrum of the adduct LiAlH4,NEt3 suggests

159~

that

it

is

actually a complex of Et,N,AlH, and LiH. Clear, relatively stable solu-

tions of aluminium hydride,162 prepared from

100%

H2S0,

and LiAlH, in

tetrahydrofuran, like related alurninohydrides, are useful reducing agents for

specific organic groups.

LiAlH,

reacts

with

B2H6

in ether solution

giving

as

products LiBH, and solvated

AlH,(BH,),-,

(n

=

0,

1,

2,

3);

163a

in tetra-

hydrofuran cleavage reactions lead to alkoxyaluminium compounds believed

to be the previously reported

"

triple metal hydrides."

LiAlH,

reduces

aluminium halides in a stepwise manner, giving hydridoaluminium halides,

which have been characterised as triethylamine adducts

;

16Xb

these presum-

ably constitute the so-called

"

mixed hydride

"

reagents. Aluminium boro-

hydride complexes

with

Et,N

[Et,N,Al(BH,),H]

164a

and ethers

(e.g.,

H2AlBH4,2THF) have been characterised

;

in crystalline Me,N,Al(

BH,),

at low temperatures the aluminium is surrounded by

a

distorted pentagonal

bipyramidal array

of

ligands,l6& whereas at room temperature the con-

figuration is essentially tetrahedral.

A remarkable compound &,B(NMe,),Me,, formed from trimethyl-

aluminium and B2(NMe2),, may be the first example

of

a

compound con-

taining

Al-Al

bonds;

1e5

(19)

repreBents

a

possible structure.

So-called

"

isosteres

"

of tris(trimethylsily1)amine have been prepared in which

two

of

the SiMe, groups are replaced by PMe, and MMe, (where

M

=

Al,

Ga,

or

In)

,166

Properties of these compounds indicate the following order of acceptor

strengths

:

Me,Al> Me,Ga> Me31n. The Si-8-4 skeleton of Me,Si-8-AlEt,

(prepared from Me,SiF and AlEt,)

16'

is isoelectronic not

only

with the

Al-F-A1

unit of [Et,Al-3'-AlEt,]- but with the Si-0-Xi unit

of

siloxanes,

Aluminium.

1965,

122,

116;

(c)

G.

Will,

Nature,

1966,

212,

175;

(d)

V.

I.

Matkovich,

J.

Economy,

R.

F.

Giese,

jun.,

and

R.

Barrett,

Acta Cryst.,

1965,

19,

1056;

(e)

R.

Naslain and

J.

gtourneau,

Compt. rend.,

Xer.

C,

1966,

263,

484.

159

(a)

E.

C.

Ashby,

Adv.

Inorg. Chem. Rudiochem.,

1966,

8,

283;

(6)

E.

C.

Ashby

and

P.

Kobetz,

Inorg. Chew.,

1966,

5,

1615;

R.

Ehrlich, A.

R.

Young,

11,

G.

Rice,

J.

Dvorak,

P.

Shapiro,

and

H.

F.

Smith,

J.

Amer.

Chem.

Xoc.,

1966,88,

858;

(c)

R.

Ehrlich

and

G.

Rice,

Inorg. Chem.,

1966,

5,

1284.

160

R.

Koster

and

P.

Binger,

Adv.

Inorg.

Chem. Radiochem.,

1965,

7,

263.

lG1

G.

Fritz,

Angew. Chem., Internat.

Edn.,

1966,

5,

53.

lea

H.

C.

Brown,

P.

M.

Weissmm,

and

N.

M.

Yoon,

J.

Amer.

Chem.

SOC.,

1966,

88,

1458;

H.

C.

Brown

and

N.

M.

Yoon,

ibid.,

p.

1464.

16s

(a)

E.

C.

Ashby and

W.

E.

Foster,

J.

Amr.

Ohem. Soc.,

1966,

88,

3248;

(b)

E.

C.

Ashby and

J.

Prather,

ibid.,

p.

729.

lti4

(a)

R.

Ehrlich and

A.

R.

Young,

11,

J.

Inorg.

Nuclear Chem.,

1966,

28,

670;

(b)

H.

Noth

and

H.

Suchy,

J.

Orgunometallic Chem.,

1966,5, 197;

(c)

N.

A.

Bailey,

P.

H.

Bird,

and

M.

C.

H.

Wallbridge,

Chem.

Comna.,

1966, 286.

165

E.

P.

Schram,

Inorg. Chem.,

1966,

5,

1291.

166

H.

Schmidbaur and W. Wolfsberger,

A.ngew.

Chem.,

Internat.

Edn.,

1966,

5,

312.

167

H.

Schmidbaur and

H.

F.

Klein,

Angew.

Ch.,

Internat.

Ed%,

1966,5,726.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

DOWNS,

EBSWORTH

AND

TURNER:

THE

TYPICAL

ELEMENTS

157

and

is

probably linear

or

nearly

so.

A

ring structure with

Al-F-Al

bonding

is

indicated for diethylaluminium fluoride,l** which is tetrameric

in

benzene

solution. Dialkylaluminium cyanides (Me,AlCN and Et,AlCN)

lSgO

and

azides (Et2AlN3)

lSgb

are also associated under normal conditions, with

degrees of aggregation ranging from

3

to

8.

Reports

of

new organoalllminium

compounds relate,

inter

alia,

to 5-membered

Al-C

heterocycles,1700

aluminium-methylene compounds Y2Al-CH,*AlY,

(Y

=

C1

or

Et),l7M

alkali diethylalumino-aromatic complexes,l7~ and

alkyl(organosily1amino)-

aluminium deri~atives.170~ Insertion

of

CH,

occurs

170e

when diazomethane

reacts with organoalanes, a process in which aluminium-ylides

(

R,Al-.

CH,+)

may well be intermediates.

1

:

1

Complexes of CpzWH2 and Cp,ReH

(Cp

=

n-C5H5) with me, (but not with BMe,

or

GaMe,) have been

is01ated.l'~

/Al

\

0

yo-

yo\

I

I

Si,R3

MeZSi SiMel

I

1

\o'

Me2Si

SiMez

(2')

The molecules of some dialkylaluminium alkoxides contain 4-

or

6-

membered

Al-0

rings, according to spectroscopic premises

;172s

173a

4-membered rings also form the basis of several newly characterised

aluminosiloxanes (structure

XX

where

X

=

Me,

R

=

Me;173u

X

=

Me,

R

=

Ph;173a

X

=

Br,

R

=

Me;173b

X

=

Me,

R

=

H

17%).

A

compound

C,H,,A13Br50,Si,, formed by the reaction of

octamethylcyclotetrasiloxane

with aluminium bromide

or

trimethylsiloxyaluminium

dibromide,

has

the

structure

(21)

with a polycyclic system centred on a single 5-co-ordinate

aluminium at0rn.l7~~ Sublimation of the adduct &(NO3),,N.& obtained

from

Al(N0,),,9Hz0

and

N205,

gives anhydrous &(NO,),,

from

which salts

of

the

[Al(NO,),]-

anion have been prepared.l7*

Of the two ions identified

16@

(a)

R.

Ehrlich

and

A.

R.

Young,

11,

J. Inorg. Nuclear Chem.,

1966,

28,

674;

(6)

K.

Dehnicke,

J.

Striihle,

D.

Seybold, and

J.

Miiller,

J. Organometallic

Chm.,

1966,

6,

298.

170 (a)

J.

J.

Eisch and

W.

C.

Kaska,

J.

Amer. Chena.rSoc.,

1966,88,2976;

H.

Lehmkuhl,

Angew. Chem., Internat. Edn.,

1966,

5,

663;

(b)

H.

Lehmkuhl and

R.

Schafer,

Tetra-

hedron Letters,

1966, 2315;

(c)

H.

Lehmlruhl,

Tetrahedron Letters,

1966, 2811, 2817;

(d)

D.

Ya.

Zhinkjn,

G.

K.

Korneeva, N.

N.

Korneev,

and

M.

V.

Sobolevskii,

J.

Gem

Chem.

(U.S.S.R.),

1966,

36,

360;

(e)

H.

Hoberg,

Annalen,

1966, 695, 1.

171

H.

Brunner,

P.

C.

Wailes, and

H.

D.

Kaesz,

Inorg. Nuclear

Chem.

Letters,

1965,

1,

125.

17~

R.

Tarao,

Bull.

Chem.

SOC.

Japan,

1966,

39,

725,

2126.

17*

(a)

H.

Schmidbaur and

F.

Schindler,

Chem. Ber.,

1966,99,2178;

(b)

M.

Bonamico,

G.

Dessy,

and

C.

Ercolani,

Chem. Comm.,

1966, 24;

(c)

J.

F.

Salmon,

S.

J.

Evers,

and

E.

C.

Evers,

J.

Inorg. Nuclear Chem.,

1966,

28,

2787;

(d)

M.

Bonamico,

Chem.

Comm.,

1966, 135;

C.

Ercolani,

A.

Camilli,

and

G.

Sartori,

J.

Chem. Soc.

(A),

1966, 606.

A.

W.

Laubengayer and

G.

F.

Lengnick,

Inorg. Chem.,

1966,

5,

603.

C. C.

Addison,

P.

M.

Boorman, and

N.

Logan,

J.

Chem.

SOC.

(A),

1966, 1434.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

158

INORGANIC CHEMISTRY

by the vibrational spectra

of

alkaline aluminate

solution^,^^^

the one pre-

dominating at pH>13isA102- (withDwhsymmetry), whilst that predominat-

ing at pH

8-12

is

either square-planar

Az(

OH),-

or, more likely, a polymeric

species built up from

&(OH),

octahedra.

Gallium,

Indium,

and

Thallium.

A

new monograph deals with the

chemistry

of

gallium.176 The short-lived cations TIZ+ and

T1,+

have been

identified in aqueous solution by pulse radiolysis.177 Compounds containing

metal-metal bonds include the novel tetracarbonylcobalt derivatives,

e.g.,

X,M[CO(CO),]~-,,

(X

=

halogen;

M

=

Gay

In, or T1)

l7sU

resulting from

halide displacement

or

insertion reactions

of

tetracarbonylcobalt species, and

T1(SiEtJ3 and T1(GeEt3)3.17gb The crystal structure

of

the room-temperature

modification of InCl implies

17&

at least incipient metal-cluster formation,

l151n

n.m.r. spectra

of

aqueous solutions

of

indium compounds afford

information

179

about complex-formation and exchange processes. Relative

donor strengths with respect

to

GaH3 have been assessed qualitatively by

displacement reactions

;

intramolecular hydrogen-elimination from the

adducts Me2n!tE€,GaH3

(M

=

N

or

P)

gives Me2MGaH2,

of

which the di-

methylamino-compound is dimeric

in

benzene, but apparently monomeric in

the gas phase.lg00 The H-Ga bond

of

HGaCl, adds across double bonds,

giving organogallium derivatives

("

hydrogallination

").1SOb

Four-membered

GeO

and

In-0

rings analogous to

XX

constitute the

framework of a number of compounds of the type

[X,M-0-MR,],

(where

M

=

Ga

or

In;

X

=

Me or C1;

M

=

C, Si,

or

Ge;

R

=

Me

or

Ph),1730,

lgla#

formed, for example, by the reaction of trialkyl-gallium or -indium etherates

with triorganosilanols. Organogallium dihalides are conveniently prepared

by the reaction

of

organosilanes

or

-germanes with gallium halides.

lglb

Electrical properties

of

In-InC1, melts support

1*2a

the existence

of

InC1,

In2Cl3,

and InCl,,

of

which only the InCl melt contains simple

ions.

Vi-

brational spectra,

of

gallium tri-chloride, -bromide, and -iodide comply with

a

dimeric molecular structure in the solid and liquid phases.182b The prepara-

tion and properties

of

oxyhalides

of

gallium and indium,lg2d

of

the

thermally stable thallium compounds Tl,SCl, and T1,SeCl,,1s2B and

of

anionic In-F complexes

ls2f

are described.

A

variety of adducts

of

indium(m) and thallium(rn) halides has been

176

L.

A.

Carreira,

V.

A.

Maroni,

J.

W.

Swaine,

jun.,

and

R.

C.

Plumb,

J.

Chem.

Phys.,

1966,

45,

2216.

170

I.

A.

Sheka,

I.

S.

Chaus, and T. T. Mityureva,

"

The

Chemistry

of

Gallium

"

(Monograph

6;

Topics

in

Inorganio and Generd Chemistry), Elsevier,

1966.

If7

B.

Cercek,

M.

Ebert, and

A.

J.

Swallow,

J.

Chem.

SOC.

(A),

1966, 612.

178

(a)

D.

J.

Patmore

and

W.

A.

G.

Graham,

Inorg.

Chem.,

1966,

5,

1586;

(b)

N.

S.

Vyazankin,

E.

V.

Mitrofmova,

0.

A.

Kruglaya,

and

G.

A.

Razuvmv,

J.

Qen.

Chem.

(U.S.S.R.),

1966,

36,

166;

(c)

J.

M.

Van

den

Berg,

Actu

C~yst.,

1966,

20,

905.

179

T.

H.

Cannon

and

R.

E.

Richards,

Tram.

Purduy

SOC.,

1966,62, 1378.

l80

(a)

N.

N.

Greenwood,

E.

J.

F.

Rosa,

and

A.

Storr,

J.

Chem.

SOC.

(A),

1966, 706;

(b)

H.

Schmidbaur

and

H.

F.

Klein,

Angew.

Chem.,

Internat.

Edn.,

1966,

5,

312.

lE1

(a)

H.

Schmidbaur and

B.

her,

Angew.

Chm.,

Inte4.nat.

Edn.,

1966,

5,

313;

(b)

H.

Schmidbaur

and

W.

Findeiss,

Chem.

Ber.,

1966,99,2187.

(a)

V.

N.

Fadeev

and

P.

I.

Fedorov,

Rws.

J.

Inmg.

Chem.,

1965,

10,

788;

(b)

A.

Balls,

A.

J.

Downs,

N. N.

Greenwood, and

B.

P.

Straughan,

Trans.

Furaduy

SOC.,

1966,

62,

521;

(c)

F.

M.

Brewer,

P.

L.

Goggin and

G.

S.

Reddy,

J.

Inorg.

Nuclear

Chem.,

1966,

28,

361;

(d)

P.

I,.

Goggin,

I.

J.

McCoh,

and

R.

Shore,

J.

Chem.

SOC.

(A),

1966,

1004;

(e)

V.

I.

Rigin

and

S. S.

Katsanov,

Russ.

J. Inorg.

Chem.,

1965, 10,950;

(f)

E.

N.

Deichman and

L.

S.

Krysina,

ibid.,

p.

256.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

DOWNS,

EBSWORTH

AND

TURNER:

THE

TYPICAL

ELEMENTS

159

characterised.183u Physical properties, such as conductivities in non-

aqueous solution and

i.r.

spectra, form the basis

of

assignments to either

molecular

(e.g.,

GaX,,L, where

X

=

C1,

Br,

I;

L

=

unidentate base)

or

ionic (e.g.

[T1(pyridine),C1,]+~Cl4]-)

structures for these and similar com-

plexe~.~83~,

b

Relative donor and acceptor strengths,

vix.,

N

>

S

>

0

and

GaCl,

>

GaBr,

>

GaI,, based

on

thermochemical and n.m.r. measurements

on

some

1

:

1

gallium trihalide adducts, are related

18%

to

steric and polari-

sability effects. Spectroscopic results suggest that the

C-T1-C

skeleton

of

dialkylthallium cations

is

linear when coordinated by oxygen donors but

bent when co-ordinated by pyridine.

Group

IV.-Ca&n.

The

CF,

radical

is

pyramidal

in

thevapour phase1g4a

and in matrices,1g4b in contrast to the planar CH,; the angle

lg5

in

CF,

is

104.9".

Methods

of

making graphitic oxide have been compared and im-

proved; carbon grains react with incandescence with

NF,

in a

Ni

tube

186b

at

150",

and an explosion occurred when activated charcoal was treated with

NF,

at

low temperature. Equimolar adducts

of

R&oF

and

MF',

(M

=

P,

As,

Sb)

have been prepared, which are volatile and appear to change from

molecular to ionic

forms

at

low

temperatures;1*7

CCI, and

Bu4NC1

give a

yellow solid adduct, formulated

188

as

containing CCl,-. The heat

of

forma-

tion

of

thiocyan~gen,~~~~ and pKu values

18gb

for

HX

(X

=

NCO,

NCS,

NCSe,

NNN),

have been measured. The action

of

HC1

on

NaOCN

at

-80"

gives

lgoU

HNCO

containing

ca.

3%

HOCN;

the infrared spectrum

of

gaseous

fulminic acid indicates

190b

that the

H

is bound to

C.

Carbonyl isocyanate

has been made by the thermal decomposition

of

trichloroisocyanuric acid

;l9lu

the action of boiling

CC1,

on (SbC14N3)2 gives

191b

[C(N,),]+sbC16-.

The reactions of elementary silicon

have

been reviewed.lQ2

Photolysis

of

silyl

azide at

4°K

gives a species identified by infrared spectro-

scopy

lQSU

as HNSi; the e.s.r. spectrum of the SiH, radical, formed

in

a

Kr

matrix at

4"K,

indicates that the species is ~yramidal,l93~ as (probably) are

GeH,

and SnH,. The lower hydrides produced by the action of

aqueous,

ethanolic,

or

ammoniacal acids on

CaM

or Ca,M

(M

=

Si

or

Ge) are of

formulae

SiR,.,,

and GeH,.9-1.2; the reported formation

of

MH,

has not

(a)

A.

J.

Carty and D.

G.

Tuck,

J.

Chem.

Xoc.

(A),

1966, 1081;

B.

F.

G.

Johnson

and

R.

A.

Walton,

Inorg.

Chem.,

1966,

5,

49;

(b)

W.

R.

McWhinnie,

J.

Chem.

SOC.

(A),

1966, 889;

N.

N.

Greenwood,

T.

S.

Srivastava, and B.

P.

Straughan,

ibid.,

p.

699;

(c)

N.

N.

Greenwood and

T.

S.

Srivastava,

ibid.,

pp.

267, 270, 703;

(d)

G.

D.

Shier

and

It.

S.

Drago,

J.

OrganmetaZlic Chern.,

1966,

5,

330.

lS4

(a)

G.

A.

Carlson

and

G.

C.

Pimentel,

J.

Chem.

Phys.,

1966,

44,

4053;

(b)

D.

E.

Milligan,

M.

E.

Jacox, and

J.

J.

Corneford,

ibid.,

p.

4058.

F.

X.

Powell and D.

R.

Lide,

J.

Chem.

Phy.,

1966,

45,

1067.

186

(a)

H.

P.

Boehm

and

W.

Scholz,

Annalen,

1966, 691, 1;

(b)

J.

Massonne and

R.

Holst,

Angew.

Chem.,

Internat. Ed%.,

1966,

5,

317.

E.

Lindner and

H.

Kranz,

Clzem. Ber.,

1966,

99, 3800.

lBS

D.

H.

McDaniel and

R.

M.

Dieters,

J.

Amer.

Chem.

SOC.,

1966,

88,

2607.

(a)

C.

E.

Vanderzee

and

A.

S.

Quist,

Inorg. Chem.,

1966,

5,

1238;

(b)

J.

H.

Boughton and

R.

N.

Koller,

J.

Inorg.

Nuclear

Chem.,

1966,

28,

2851.

lgo

(a)

N.

Groving

and

A.

Holm,

Acta

Chem.

Xcand.,

1965,

19,

1768;

(b)

W.

Beck

and

I<.

Feldl,

Angew.

Chem.,

Internat. Edn.,

1966,

5,

722.

lg1

(a)

E.

Nachbaur,

Monatsh.,

1966,97,361;

(b)

U.

Muller

and

R.

Dehnicke,

Angew.

Chem.,

Internat.

Edn.,

1966,

5,

841.

lga

E.

Bonitz,

Angew. Chem., Internat. Edn.,

1966,

5,

462.

lea

(a)

J.

F.

Ogilvie and

S.

Cradoclr,

Chem.

Conam.,

1966,

364;

(b)

R.

L.

Morehouse,

J.

J.

Christiansen, and

W.

Gordy,

J.

Chm.

Phys.,

1966,

45,

1751.

Silicon.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

160 INORQANIC

CHPJMISTBY

been confirmed.104

In

SiF,,

the microwave spectrum leads

to

a bond anglelO5Q

of

100'59';

the reactions of the species

in

matrices at low temperatures

lQSb

and with unsaturated systemsl0& have been investigated. The Me,Si

radical, generated by the thermal decomposition of (Me,Si),Hg, extracts

oxygen

or

halogen

atoms

from

organic

solvent^.^^^

The relationship between

(p4)n-bonding and bond angles in (SiH&N and related species has been

discus~ed.~~7 Microwave spectroscopy shows that

the

&eleton

of

SiH3NC0

is linear;lOsa electron diffraction, however, indicates that Me,SiNCX

(X

=

0

or

S)

is bent at

N.lOsb

The shifts to higher energies

in

the

U.V.

spectra

of

(SiH,),Z

(Z

=

Cl,

0,

N)

when compared with

(CH3),Z

are consistent with

(p+d)

n-bonding

in

the former species.lo9 The large shifts200a

to

lower

energies

in

the

(n-n*)

transitions

of

R,MCOR

as

M

changes from

C

to Si,

Ge,

or

Sn have been

put

down

largely to inductive electron release, rather

than to n-interactions, and evidence as to the basicities

of

the ketones

concerned is cited

in

support.200b In

Pt(@

complexes the exceptionally low

values forv(Pt-X)

(X

=

C1 or

Br)

tram

to

R3S

or R3Ge have been interpreted

as

indicating that Si has the largest

known

trans

effect

of

inductive origin.

Additivity parameters for heats of formation of organosilicon compounds

have been discussed,202 and values

for

a number

of

bond energies

203a

and

bond dissociation energies

203b

involving Si,

Ge,

and Sn have been reported.

Controversy continues

204a

over the value

of

D(Si-Si)

in

Me,Si,.

In

SiH3GeH3, mass spectrometry

204b

leads to

a

value for D(Si-Ge) of

99.9

kcal., whilst a thermochernical method

20gc

gives E(Si-Go)

as

42.5

kcal.

Exchange reactions at Si and Ge have been extensively studied;205" exchange

involves halogen

205b

and pseudohalogen

205c

groups, oxygen, nitrogen,20Sd

and (in the presence of AlC1,) methyl groups.2o5s

Si

lylpotassium reacts with monochloro-N- dialkylaminoboranes and trial-

19*

9.

Royen and

C.

Rockthchel,

2.

anorg. Ch.,

1966,

346,

279.

195

(a)

V.

M.

Rao,

R.

F.

Curl,

P.

L.

Timms,

and

J.

L.

Margrave,

J.

Chem. Phys.,

1965,43, 2557;

(b)

J.

M.

Bassler,

P.

L.

Timms,

and

J.

L.

Margrave,

Inorg.

Chm.,

1966,

5,729;

(c)

P.

L.

Timms,

D.

D.

Stump,

R.

A.

Kent,

and

J.

L.

Margrave,

J.

Amer.

Cham.

Soc.,

1966,

88,

940;

J.

C.

Thompson,

J.

L.

Margrave,

and

P.

L.

Timma,

Chem. Comm.,

1966, 566.

lg6

A.

G.

Beaumont,

C.

Eaborn,

R.

A.

Jackson, and

A.

W.

Walsingham,

J.

Organo-

metallic

Chern.,

1966,

6,

297.

lo7

E.

A.

V.

Ebsworth,

Chem.

Comm.,

1966,530;

E.

W.

Randall and

J.

J.

Zuckennan,

ibid.,

p.

732.

lQ8

(a)

M.

C.

L.

Gerry,

J.

C.

Thompson,

and

T.

M.

Sugden,

Nature,

1966,

211,

846;

(b)

K. Kimura,

IF.

Katada, and

S.

H.

Bauer,

J.

Amer.

Chm.

SOC.,

1966,

88,

416.

199

S.

Bell and

A.

D.

Walsh,

Trans. Faraday

SOC.,

1966,

62,

3005.

(a)

G.

J.

D.

Peddle,

J.

Orgametallic

Chem.,

1966,

5,

486;

(b)

K.

C.

Yates and

F.

Agolini,

Canad.

J.

Chem.,

1966,

44,

2229.

801

J.

Chatt,

C.

Eaborn, and

S.

Ibekwe,

Chem. Comm.,

1966,

700.

202

H.

E.

O'Neal and

M.

A.

Ring,

Inorg.

Chem.,

1966,

5,

435.

203

(a)

A.

Beezer

and C.

T.

Mortimer,

J.

Chem.

SOC.

(A),

1966, 514;

(b)

G.

W.

Hess,

F.

W. Lampe, and

A.

L.

Yergey,

Ann.

New

York

Acad.

Sci.,

1966,

186,

106.

304

(a)

J.

A.

Connor, G.

Finney,

G.

J.

Leigh,

R.

N.

Haszeldine,

P.

J.

Robinson,

R.

D.

Sedgwick, and R.

F.

Simmons,

Chm.

Comm.,

1966, 178;

I.

M.

T.

Davidson and

I.

L.

Stephenson,

ibid.,

p.

746;

(b)

F.

E.

SaaKeld and

H.

J.

Svec,

J.

Phys.

Chem.,

1966,

70,

1753;

(c)

S.

R.

Gunn

and

J.

H.

Kindsvater,

ibid.,

p.

1751.

205

(a)

K. Moedritzer,

Orgartometatiic

Chem.

Rev.,

1966,

1,

179;

(b)

J.

R.

van Wazer,

K.

Moedritzer,

and

L.

C.

D.

Groenweghe,

J.

Organometallic Ch.,

1966,

5,

420;

(c)

K.

Moedritzer and

J.

R.

van Wazer,

{bid.,

1966,6,242;

(d)

J.

F.

Klebe,

H.

Finkbeher,

and

D.

M.

White,

J.

Amer.

Chem.

SOC.,

1966,

88,

3390;

(e)

H.

Sakurai,

K.

Tomhaga,

T.

Watanabe, and

M.

Kumada,

Tetrahedron Letters,

1966, 5493.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

DOWNS,

EBSWORTH

AND

TURNER: THE TYPICAL ELEMENTS

161

kylamine adducts

of

monochloroboranes

to

give

silyl-N-dialkylaminoboranes

[e.g.,

SiH,B(NMe,),]

or

adducts

of

silylboranes

[e.g.,

SiH3BH2,NEt3]

;

with

chloroboranes,

or

with

dichloro-N-dialkylaminoboranes,

unstable species are

formed.206a Triphenylsilyl-lithium reacts with chloro-N-dialkylamino-

boranes to give

triphenylsilyl-N-dialkylaminoboranes,

which are also obtained

from R,SiCl, (R2N),BC1, and potassium; silylboranes were not obtained

from reactions with

B-alkyl-chloroboranes.206b

Bis(triphenylsily1)mer-

cury,2060

bis(triethylsilyl)cadmium,206d

and

tris(triethylsily1)thallium

and

its

germyl analogue

178b

have been prepared. Details

of

the determination of the

absolute configuration

of

l-naphthylphenylmethylsilane

and

of

its

fluoride

have been gi~en.~07 Ethyl-lithium reacts with disilane

to

give ethyldisi-

laneY2Osa which reacts with

KH,

forming EtSiH, and

SiH4;

the Si-Si bond

in

disilane breaks

in

the presence

of

LiX

(X

I=

C1,

Br,I).20sa

The chemistry

of

compounds containing

M-M

bonds

(M

=

Si, Ge,

Sn,

Pb) has been

reviewed;209 the e.8.r. spectrum of cyclo-Me@,- shows that the protons, the

carbon atoms, and the silicon atoms comprise equivalent sets

;210

methylated

linear polysilanes have been prepared

211a

up

to Me2,Si12, and methods

of

preparing species containing highly branched Si chains have been described.2llb

Ph

S'-

SiPhz

Ph2Si

SiPh;!

\/

21'

I

Ph2Si

-

SiPhz

Ph2Si

-

SiPhz

II

(22)

Q

(23)

The compound

(22)

reacts with lithium followed by

QC1,

(Q

=

S,

PhP,

Ph,Si, Ph2Ge, Ph,Sn) giving

212

the heterocyclic compounds

(23).

The

elusive (SiH,),NH has been prepared from ammonia and Ph2NSiH3, and

some

of its reactions have been studied;21s the action

of

ammonia

on

(Si€€,),N

gives

214

(SiH3NSiHZ),.

Bis(trimethylsily1)amine

forms

1

:

1

adducts with

AlC1,

and GaC1, that are associated

in

benzene, but the adduct (Me,Si),N,AlCl,

is

partly dissociated

in

that solvent

into

its

components.21Ku Stable adducts

of SnCl, with (Me,SiNH),, (Me,Si)&F€, and Me3SiNMez have been~repared.~15~

The action of

SOCI,

on

(Me,Si),N gives

216

Me,SiNSO. Dimethylamine

806

(a)

E.

Amberger

and

R.

Romer,

2.

unorg.

Chem.,

1966,

345,

1

;

(b)

H.

Noth

and

G.

Hollerer,

Chem.

Ber.,

1966,

99,

2197;

(c)

R.

A. Jackson,

Chem. Comm.,

1966, 827;

(d)

N.

S.

Vyazankin,

G.

A.

Razuvaev, and

V.

T.

Bychkov,

J.

en.

Chem.

(U.S.S.R.),

1965,

35,

394.

(a)

W.

J.

Bolduc and

M.

A.

Ring,

J.

OrganometaZZic

Chem.,

1966,

6,

202;

(b)

R.

C.

Kennedy,

L.

P.

Freeman,

A.

P.

Fox,

and

M.

A.

Ring,

J.

Inorg.

Nuclear

Chem.,

1966,

28,

1373.

aos

H.

Gilman,

W.

H.

Atwell, and

F.

K.

Cartledge,

Adv.

Organornetdic

Chem.,

1966,

4,

1.

alo

G.

R.

Husk

and

R.

West,

J.

Amer.

Chm.

Soc.,

1965,

87,

3993.

*11

(a)

M.

Kumada,

M.

Ishikawa,

and

S.

Maeda,

J.

Organometa& Chem.,

1966,

5,

120;

(b)

H.

Gilman and R.

L.

Harrell,

ibid.,

p.

199.

al*

E.

Hengge

and

U.

Brychey,

Nonut&.,

1966,

97,

1309.

%14

R. L.

Wells

and R. Schaeffer,

J.

Amer.

Chem.

SOC.,

1966,

88,

37.

p16

(a),

N.

Wiberg and

K.

H.

Schmid,

2.

unorg.

Chm.,

1966,

345,

93;

(b)

M.

F.

I1@

0.

J. Scherer and

P.

Hornig,

Angew.

Chem.,

Internat.

Edn.,

1966,

5,

729.

a07

Y.

Okaya

and

T.

Ashida,

Acta

Cryst.,

1966, 20,461.

B.

J.

Aylett and

M.

J.

Hakim,

Inorg.

Chm.,

1966,

5,

167.

Lappert

and

G.

Srivastava,

Inorg.

Nuclear

Chm.

Letters,

1965,1, 63.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

162

INORGANIC

CHEMISTRY

reacts

217

with Si2C1, to form (Me,N),Si2; the compound Ph,SXElCl

is

formed

21g

as an intermediate in the production of Ph,SiNC12 from Ph,SiNH,

and Me3COC1. Interest in

silyl

derivatives of hydrazine

is

maintained;

21Q0

the structures

of

the isomeric hydrazine derivatives (Me,Si),N,H, have been

reassigned on the basis of spectroscopic evidence, and several new species

(

R3Si)2N2Ha have been prepared.21Qb Amines containing

SiF,

groups

have

been made from the amine adducts

of

SiF,, and some

of

their properties

have been reported.220 Triphenylsilyl azide reacts with PhpP2 to give221

Ph,SiN*PPh,*PPh,*NSiPh,;

the compound Me,SmPMe,, made

from

Me,SiN3 and PMe,, forms

1

:

1

adducts1G6 with MMe,

(M

=

Al,

Gay

In).

The series

of

compounds

222

[Me,Si(Me)N],IMMe,-,

(n

=

1-43;

M

=

As,

Sb,

Bi)

has been made

from

Me,SiN(Me)Li and Me,,MX,

(X

=

C1 or Br).

The

chemistry

of

SiN

heterocycles has been reviewed;223a species containing

the

ring system

(24)

have been synthesized

223b

from R,"SiCl*SiR,"Cl and

R,Si(NLiR')

2.

Si

R'

'R'

(2s)

The formation and reactions of Si-P compounds have been discussed;Is1

silylphosphine gives an adduct with

BE',

at

-

134"

that decomposes at higher

temperatures,

SiH3F'

and (SiR,),P being among the products.224~

AlkaIi

metal

mercaptides replace R,Si

or

R3Sn

groups bound

to

phosphorus partly or com-

pletely by

RS

gr0ups;2~4~ Me,SiP(SEt), has been made from (Me,Si),P

and

(SEt),.

The compounds (Et3M)3M

(M

=

Si, Ge, Sn;

M'

=

Sb, Bi) have been

prepared

225

from Et,MH and Et,M'.

The

compound Me,SiAsMe, gives

wb

Me,AsC(S)S-SiMe, with

CS,,

and forms a

1

:

1

adduct with

HBr.

The action of chlorine on R,SiONa gives R,SiOCI, and not (as reported)

a

a17

E.

Wiberg,

0.

Stecher,

and

A.

Neumaier,

ImTg.

Nuclear

Chem. Letters,

1965,1,33.

218

P.

Bekiaroglou,

2.

anorg.

Chern.,

1966,

345,

290.

21a

(a)

U.

Wannagat,

G.

Schreher,

0.

Brandstiitter, and

1\6.

Peach,

Monatsh.,

1965,

98,1902;

F.

Hofler

and

U.

Wannagat,

ibid.,

1966,97,1598;

(b)

U.

Wannagat,

F.

Hbfler,

and

H.

Biirger,

ibid.,

1965,

96,

2038;

R.

West, M. Ishikawa, and

R.

E.

Bailey,

J.

Amer.

Chem.

Soc.,

1966, 88,4648.

azo

M.

Allan, B.

J.

Aylett and

I.

A.

Ellis,

Inorg.

Nzcckar

Chm.

Letters,

1966,

2,

261;

Chem.

and

Ind.,

1966, 1417.

zal

K.

L.

Paciorek and

R.

H.

Kratzer,

J.

Org.

Chem.,

1966,

81,

2426.

22a

0.

J.

Scherer,

P.

Hornig,

and

M.

Schmidt,

J.

Organometdlic Chem., 1966, 6,269.

2z3

(a)

W.

Fink,

Angew. Chem., Internat. Edn.,

1966,

5,

760;

(b)

U.

Wannagat

and

0.

Brandstiitter,

Monatsh.,

1966, 97, 1352.

224

(a)

C.

R.

Russ

and A.

G.

MacDidd,

Angew. Chem., Internat.

Edn.,

1966,

6,

41

8

;

(b)

A.

B.

Brucker,

L.

D.

Balmhova,

and

L.

Z.

Soborovskii,

J.

Gen.

Chem.

(U.S.S.R.),

1966,

36,

79.

N.

8.

Vyazankin,

G.

A.

Razuvaev,

0.

A.

Kruglaya, and

G.

S.

Semchikova,

J.

Organometallic Chem.,

1966, 6, 474.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

DOWNS,

EBSWORTH

AND

TURNER:

THE

TYPICAL

ELEMENTS

163

peroxy-~pecies;~~0~ the hypochlorite adds to Ph,As and Ph,Sb.

The dimers

(Me,SiOAlBr,),

and

(Me,SiOAlMe,), contain the expected planar 4-mem-

bered

Al-0-Si

ring

structures. Sodium trimethylsilanolate reacts with

Me2AuBr

to

give

2~

Me,SiOAUMe,. Silanols react

227a

with perfluoracetone,

giving

(CF3),C(

OH)OSiR,.

In

the presence of HgI,, CH,:C(OMe)OSiEt,

rearranges

2278

to Et,SiCH2C02Me. The properties of Si-S compounds have

been reviewed;228u silicon

is

displaced from

(25)

by the halides of metal-

loids

228b

such as

By

P,

As,

Sb,

and Sn.

A

compound containing sulphur bound

to an asymmetric silicon centre has been prepared, and some of its reactions

investigated.22& Compounds

of

formulae

(RSi),M,

(M

=

S

or

Se), believed

to have adamantane-like structures, have been made from RSiCl, and

H2M;

with RSnCl,, however, products

(RSn),S,

are formed.229

Phase studies

230

indicate that the only binary Si-Te species formed

in

the solid state

is

Si,Te,.

Refluxing

of

Ph,Si with

Co2(CO)8

gives [(CO),Co,Si],; compounds con-

taining Me,Si and Me,Ge groups bound

to

platinum have been ~repared.231~

The electrochemistry

of

Ph,M derivatives

(M

=

Si,

Ge,

Sn)

has been

in-

vestigated.la, The formation and properties

of

organofluorosilicates has

been reviewed

;232a

aqueous SbF, reacts with organofluorosilicates

2~

to

form R,Sb. Methylchlorosilanes form adducts with HCl and tetraalkylam-

monium halides.

255

Trimethylamine and HCF2CF2SiH, give an equimolar

adduct, liquid at room temperature, that

is

believed

to

contain 5-co-ordinated

silicon.

234

Germanium.

In

the crystal, GeF,

is

a fluorine-bridged chain polymer,

with weak fluorine bridges between ~hains.2~~ The solubility of GeO,

in

acids and bases has been st~died;2~6U the overall hydrolysis constant of

GeXe2-

to Ge02(hex.) is given by log

K288

=

-25-8&-0*3,

and the hydrolytic

equilibria have been discus~ed.2~~~ Complex compounds

of

germanium, and

the state of germanium

in

solution, have been reviewed.23M The action

of

conc.

HIO,

or

HIO,

on

GeO,

gives basic Ge(Iv) iodate

or

peri~date.~~~~

In

(a)

J.

Dahlmann,

A. Rieche, and L. Austenat,

Angew.

Chem., Internat.

Edn.,

1966, 5,727;

(b)

H.

Schmidhaur and

M.

Bergfeld,

Img.

Chem.,

1966,

5,

2069.

827

(a)

A.

F.

Janzen and

C.

J.

Willis,

Canad.

J.

Chem., 1966,44,745;

(b)

I.

F.

Lutsenko,

Yu.

I.

Baukov,

G.

S.

Burlachenko, and

B.

N.

Khasapov,

J.

Organometallic Chem.,

1966,

5,

20.

(a)

A. Haas,

Angew.

Chem., Internat.

Edn.,

1965,

4,

1014;

(b)

E.

W.

Abel,

D.

A.

Armitage, and

R.

P.

Bush,

J.

Cltem.

SOC.,

1965, 7098;

(c)

L.

H.

Sommer

and

J.

McLick,

J.

Amer.

Chm.

SOC.,

1966,

88,

5359.

saQ

J.

A.

Forstner

and

E.

L.

Muetterties,

Inorg. Chem.,

1966,

5,

552.

8ao

L.

G.

Bailey,

J.

Phys. and

Chem.

Solids,

1966,27, 1593.

281

(a)

S.

F.

A. Kettle and

I.

A.

Khan,

J.

OrganometaWic Chern.,

1966,

5,

588;

(b)

F.

Clockling and

K.

A.

Hooton,

Ch.

Comm.,

1966, 218.

a32

(a)

R.

Miiller,

OrganometaEliG Chem.

Rev.,

1966,

1,

359;

(b)

33.

Miiller

and

C.

Dathe,

Chem. Ber.,

1966,

99,

1609.

ass

N.

M.

Alpatova,

Yu.

M.

Kessler, and A.

I.

Gorbmev,

Rws.

J.

Inorg.

Chem.,

1965,

10,

854.

a34

D.

I.

Cook,

R.

Fields,

M.

Green,

R.

N.

Haszeldine,

B.

R.

Iles,

A. Jones, and

M.

J.

Newlands,

J.

Chem.

SOC.

(A),

1966, 887.

as6

J.

Trotter,

M.

Akhtar, and

N.

Bartlett,

J.

Chem.

SOC.

(A),

1966, 30.

*3*

(a)

E.

A.

Knyazev,

I.

A. Kakovskii, and Yu.

B.

Icholmanskikh,

Rws.

J.

Iwg.

Chem.,

1965, 10, 1464;

L.

N.

Shigina and

V.

M.

Andrew,

ibid.,

1966,

11,

469;

(b!

I.

Q.

Ryss

and

N.

F.

Kulish,

ibid.,

1965,10,996;

(c)

V.

A.

Nazarenko

and A.

M.

hdrianov,

Rws.

Chena.

Rev.,

1965, 36, 547;

(d)

N.

I.

Lobanov,

Rum.

J.

Inorg. Chem.,

1966,

11,

238; (e)

R.

S.

Tobias

and

S.

Eutcheson,

J.

Orgametallic Chem.,

1966, 6, 535.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

164

INORGANIC CHEMISTRY

water, Me,Ge2+ cations are not formed; the species present

is

identified by

Raman

as

Me,Ge(OH),. The heat

of

formation

AH,02s8

of

of

GeF,

is

found

to

be

-284*37&0*15

kcal./mole

by

fluorine bomb calori-

met~y.~~~ The action

of

an electric discharge on

a

mixture of

GeH,,

SiH,, and

Si,H, has led

to

the provisional identification

of

ten new hydrides by mass

spectrometry.23s The n.m.r. spectra of R,GeH,,, andR,GeH,-,-

(n,

=

0-3)

in liquid ammonia have been measured;23B

it

is deduced that

GeH,

is

a much

stronger acid than Ph,GeH. The halides GeH,X and Ge,H,X

(X

=

C1,

Br)

have been prepared

240a

from the hydrides and

AgX;

monogermane and

CF31

give GeH,I when heated t0gether.240~ Organogermanium chemistry

has been revie~ed,~~l~ and the mass spectra

of

a

number

of

organoger-

manium species have been determined.241b Some of the simpler con-

jugated dienes react

with

GeI, to

form

5-membered ring species containing

GeI,

gr0ups;~4~" treatment of the etherate

of

HGeX,

with MeMgBr or

MeLi

gives

2*2b

Me(GeMe,),Me, (Me,Ge),, and (Me,Ge),. Hexaphenyldigermane

reacts with Sr and Ba in liquid ammonia

to

give

(Ph,Ge),M

(M

=

Sr, Ba);

the analogous zinc derivative has been made from Ph,GeNa and

ZnC1,

in

the same Some of the reactions of (Et,Ge),Cd have been

st~died.~43b Solutions

of

Ph4As+MC1,-

(M

=

Ge, Sn) in

CH,C1,

react with

BX,

(X

=

3'

or

Cl)

to

precipitate

1

:

1

adducts formulated

7w

as

Ph4As+[X,BMCl,]

-.

Improvements

in

the direct synthesis of MeGe halides

have

been

described

;244

details

of

the preparation and reactions

of

optically

active

1

-naphthylphenylethylgermyl

compounds have been given.245

In

the

crystal, Me,GeCN has the normal cyanide structure

;

in

the Gem-Ge chains,

the

Ge-N

distances are not unusually short.246 The species R,Ge.GeR,Cl are

formed

247a

from GeCl, and R,Ge,

;

potassium in hexamethylphosphotria-

mide reacts with R,Ge2

to

give high yields

247b

of R,GeK. The action

of

MH,

(M

=

P,

As)

on Me,GeNMe2

or

(Me,Ge),m

gives

(Me3Gc)3M, also

formed from Me,GeCl and Na,M in liquid ammonia;24SQ Ph,M derivatives

(M

=

Ge,

Sn,

Pb)

of

Ph,M"H,,,

(M"

=

P,

As,

Sb) have been prepared.248b

It

is deduced from the infrared spectra that the M'&'' skeletons are

pyra-

aa7

P.

Gross,

C.

Hayman, and

J.

T.

Bingham,

Tram.

Paraday

SOC.,

1966,

62,

2388.

238

T.

D.

Andrews and

C.

S.

G.

Phillips,

J.

Chem.

Soc.

(A),

1966, 46.

a40

(a)

K.

M.

Mackay,

P.

Robinson,

E.

J.

Spanier, and

A.

G.

MacDiarmid,

J.

Iwq.

Nuclear

Chem.,

1966,

28,

1377;

(b)

J.

E.

GrifEths and

A.

L.

Beach,

Canad.

J.

CTLem.,

1966,

44,

1227.

241

(a)

F.

Glockling,

Quart.

Rev.,

1966,

20,

45;

(b)

D.

B. Chambers,

F.

Glockling,

J.

R.

C.

Light, and

35.

Weston,

Chem.

Comm.,

1966, 281.

a43

(a)

P.

Mazerolles and

G.

Manuel,

BUZZ.

SOC. chim.

France,

1966, 327;

(b)

0.

M.

Nefedov and

S.

P.

Kolnesikov,

BdZ.

Awd.

Sci.

U.S.S.R.,

1966,

201.

B43

(a)

E.

Amberger,

W.

Stoeger, and

R.

Honigschmid-Grossich,

Angew.

Chi%.,

Internat.

Edn.,

1966,5,522;

(b)

N.

S.

Vyanzankin,

G.

A.

Razuvaev,

V.

T.

Bychkov,

and

V.

L.

Zvezdin,

Bull. Acad.

Sci.

U.S.S.R.,

1966, 562.

244

K.

Moedritzer,

J.

Organmetallic

Chem.,

1966,6,282;

M. Wieber,

C.

D.

Frohning,

and

M.

Schmidt,

ibid.,

p.

427.

845

C.

Eaborn,

P.

Simpson, and

I.

D.

Varma,

J.

Chern.

SOC.

(A),

1966, 1133.

a46

E.

0.

Schlemper and

D.

Britton,

Iwg.

Chem.,

1966,

5,

611.

E.

J.

Bulten

and

J.

G.

Noltes,

TetraMron

Letters,

1966,

(a)

p.

3471;

(b)

p.

4389.

348

(a)

I.

Schumann and

H.

Blau,

2.

Naturforsch.,

1966,21b, 1105;

(b)

M.

Schumann

and

M.

Schmidt,

Inorg. Nuclear Chern. Letters,

1965,

1,

1;

H.

Schumann,

P.

Schwab,

snd

M.

Schmidt,

ibid.,

1966,

2,

309;

(a)

W.

P.

Neumann,

B.

Schneider, and

R.

Sommer,

T.

Birchall and

W.

L.

Jolly,

Inorg.

Chem.,

1966,

5,

2177.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

DOWNS,

EBSWORTH

AND

TURNER:

THE

TYPICAL

ELEMENTS

165

midal. Compounds containing

Ge

bound to Sn

or

Pb

have been obtained

from R,GeH and R3M(NMe2)

(M

=

tin

24&

or

lead

248d).

The compounds

(Et,M),BiEt

3--n

(M

=

Ge

or

Sn) have been prepared.,4& Trialkylgermanols

react with gallium alkyls to give

181b

dimeric R,GeOGaR,. Triphenylgermyl

peroxide249 has been made from Ph,GeBr and

H,O,.

The complex

(Et,P),Pd(GePh,), reacts

2Ma

with

H,

under pressure at

ZOO,

giving

(Et,P),Pd(H)GePh,. The insertion of Ge(n) and Sn(n) halides into metal-

metal bonds has been further investigated.

250b

Tin.

Studies of e.m.f. in fused NaAlCl, indicate that there is a one-

electron reduction process for Sn and Pb.251

A

1

:

1

adduct

252a

is formed

between (Q,PN), and SnC1, when

Q

=

Me, but not when

Q

=

Ph

or

C1.

In

aqueous solution, complexes Sn( 0,CMe),(n-2)

-

have beenidentified

(n

=

1-3),

with polymeric species ;252b the formation constants

for

polyphosphate com-

plexes

of

Sn(n)

in

water have been mea~ured.~~~c The formation and pro-

perties of organotin cations have been reviewed.253a The Siuence of the

nature of R upon the hydrolysis of R,Sn+ and R,Sn2+ has been investigated;

the species R2SnOH+ tend

to

dimeri~e.~5~~ Anodic oxidation

in

methanol

gives Eo(SnMe3+/Me,SnSnMe,) as

+0*14l

v.254

Tetramethyltin forms

Me,SnHSO, and methane with concentrated

H2S04,

but Sn-C bonds

in

Ph-Sn compounds are all broken

;

alkyltin hydrogen sulphates and bis(

hydro-

gen sulphates) are strong bases in that solvent, probably because of proto-

nati0n.~5~ Vibrational spectra indicate that (R,Sn),M

(M

=

0,

S,

Se) are

bent

256a

at

M,

and (Me,Sn),M'

(M'

=

N,

P,

As, Sb)

are pyramidal

256b

at

M.

The failure to observe quadrupole splitting

in

the Mossbauer spectra of a

number of asymmetrically substituted Sn(rv) derivatives

257a

is

still not

fully understood, though Mossbauer data for

a

wide range of tin compounds

have been reported

;257b

there is evidence from Mossbauer spectroscopy

257c

that Sn(AlH,), is an intermediate

in

the reduction of SnCl, to SnH, by

LiAlH,.

The type of product obtained from the addition of tin hydrides

to

a/?-unsaturated ketones depends

on

the h~dride.~5~~ Very reactive com-

Annalen,

1966,

692,

1;

(d)

W.

P.

Neumann and

K.

Kiihlein,

Tetrahedron Letters,

1966,

3419;

(e)

0.

A.

Kruglaya,

N.

S.

Vyazankin, and

G.

A.

Razuvaev,

J.

Qen.

Chem.

(U.S.S.R.),

1965, 35, 392.

24v

R.

L.

Dannley and

G.

Farrant,

J.

Amer.

Chem.

SOC.,

1966,

88,

627.

250

(a)

E. H.

Brooks

and

F.

Glockling,

J.

Chem.

SOC.

(A),

1966,1241

;

(b)

D.

J.

Patmore

and

W.

A.

G.

Graham,

Imrg.

Chem.,

1966,5,1405.

251

T.

C.

F.

Munday and

J.

D.

Corbett,

Inorg.

Chem.,

1966, 5, 1263.

252

(a)

M.

F.

Lappert and G. Srivastava,

J.

Chem.

SOC.

(A),

1966, 210;

(b)

J.

D.

Donaldson and

J.

F. Knifton,

ibid.,

p.

332;

(c)

R.

E.

Mesmer and R.

R.

Irani,

J.

Inorg.

Nuclear

Chem.,

1966,

28,

493.

2S3

(a)

R.

S.

Tobias,

Organometall~ic

Chem.

Rev.,

1966,

1,

93;

(b)

R.

S.

Tobias,

H.

N.

Farrar,

M.

B.

Hughes, and B.

A.

Nevett,

Inorg.

Chem.,

1966,5,2052.

254

G.

Tagliavini and

L.

Doretti,

Chem. Comm.,

1966, 562.

R.

J.

Gillespie,

R.

Kapoor, and

E.

A.

Robinson,

Canud.

J.

Chem.,

1966, 44, 1197.

256

(a)

H.

Kriegsmann,

H.

Hoffmann, and H. Giessler,

2.

anorg.

Chern.,

1965,

341,

24;

(b)

R.

E.

Hester and

K.

Jones,

Chem.

Comm.,

1966, 317.

257

(a)

T.

C.

Gibb and

N.

N.

Greenwood,

J.

Chem.

SOC.

(A),

1966, 43;

R.

H.

Herber

and G.

I.

Parisi,

Inorg.

Chem.,

1966,

5,

769;

(b)

J.

W.

Donaldson and

B.

J.

Senior,

J.

Chem.

SOC.

(A),

1966, 1796, 1798;

D. Khristov,

Tsv.

Bouchev, and Kl. Burin,

Compt.

rend.

Acad.

bulg.

Sci.,

1966,

19,

293;

A.

J.

Bearden,

H.

S.

Marsh, and

J. J.

Zuckerman,

Inorg. Chem.,

1966, 5, 1260; (c)

Z.

Boutschev,

D.

Christov,

Kl.

Burin,

and

Iv.

Mand-

zukov,

2.

anorg.

Chem.,

1966,

347,

199.

258

(a)

M.

Pereyre and

J.

Valade,

Compt. rend.,

1965,

260,

581;

A.

J.

Leusink

and

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

166

INORQANIC

CHEMISTRY

pounds, useful as synthetic intermediates, are obtained

from

the unexpectedly

easy addition of Sn-H bonds

to

CN

in

alkylidenemalononitrile~.~5B*

The

reaction between alkyltin hydrides and R,SnX

(X

=

NR,, OR, OSnR,)

or

related species

248c,

259a

affords a means of forming Sn-Sn chains and rings,

and

is

an example

of

a

general way of forming metal-metal bonds;25gb rings

up

to (R,Sn), have been obtained

259c

thus and by catalytic dehydrogenation

of

R,SnH2. The properties

of

organic tin-nitrogen compounds have been

reviewed.26* Distannoxanes

261a

react with HSCR to give R,SnC=-CR';

with secondary amides

NHR'COX

there is a similar reaction, unless

X

$very

electronegative, when R,SnX

is

eliminated, but with primary amides

R,SnNCO

is

formed.261b Reactions between isocyanates and distannoxanes

have also been investigated.

261c

Compounds of the form (R,PS,)SnR', and

(R,PS,),SnX,

(X

=

C1,

Br)

have been obtained;262 tin-sulphur bonds are

broken by HgCl,, CdCl,, CdBr,, K2PtC14,263 and Hg(NPh*C02H)2,261b and

tin-selenium bonds

264

by

BrMn(CO),.

A

number of compounds containing

Sn bound

to

transition metals have

been

reported.265 The n-acceptor pro-

perties

of

SnQ,

(&

=

alkyl, aryl,

CT)

have been assessed

in

Q,Sn*Mn(CO),-

derivatives (by the

CO

stretching frequencies), and in

nz-

and

p-FC6H4Pt(PEt,),SnCl, (from the

F

chemical shift)

;266b

the group-SnC1,

appears

to

be a strong n-acceptor. The role

of

solvent

in

relation to the

formation of adducts

of

tin(Iv)

halides has been considered;267a the adduct

SnCl,,N,O,

is

formulated

267b

as

NO+(

SnCl,NO,)

-.

Compounds containing

(Me,SnX,)- and (Me,SnX4)2-

(X

=

F,

C1, Br) have been prepared;268Q the

adduct

2,2',2"-terpyridyl,2Me,SnC12

has been shown crystallographically

to

contain the ions (Me,Sn,terpy)+ and (Me,SnCl,)-, the methyl groups in the

latter occupying equatorial positions of the trigonal bipyramid.26*b

Lead.

The hydrolysis of Me,Pb2+ has been investigated;z69 some

associated species are formed, and Rnrna,n spectra indicate co-ordination of

J.

C.

Noltes,

Tetrahedron Letters,

1966, 2221;

(b)

W.

P.

Neumann,

R.

Sommer,

and

E.

Muller,

Angew. Chem., Internat. Edn.,

1966,

5,

514;

R.

Sommer and

W.

P.

Neumann,

ibid.,

p.

516.

259

(a)

R.

Sommer,

B. Schneider, and

W.

P. Noumann,

Aniaalen,

1966,

692,

12;

(5)

D.

J.

Cardin and

M.

F.

Lappert,

Chem.

Cornm.,

1966, 506;

(c)

W.

P.

Neumann,

J.

Pedain, and

R.

Sommer,

Annalen,

1966,

694,

9.

260

K.

Jones and

M.

F.

Lappert,

OrganometdZic Chem. Rev.,

1966,1, 67.

261

(a)

M.

F.

Shostakovskii,

N.

V.

Komarov,

I,

S.

Guseva,

V.

K.

Misyunas,

A.

M.

Sklyanova, and T.

D.

Burnashova,

DokZady

Chem.,

1966,

163,

678;

(b)

A.

G.

Davies,

T.

N.

Mitchell, and

W.

R.

Symes,

J.

Chem.

SOC.

(C),

1966,

1311;

(c)

A.

J.

Bloodworth

and

A.

G.

Davies,

ibid.,

p.

299.

F.

Bonati,

S.

Cenini, and

R.

Ugo,

Rend.

Prim0

Lembardo

Sci.

Lettere,

1965,

A,

99,

825.

E.

W.

Abel,

D.

B.

Brady, and

B.

C.

Crosse,

J.

Organometallic Chem.,

1966,

5,

260;

R.

C.

Poller

and J.

A.

Spillman,

ibid.,

1966,

6,

668.

264

E.

W.

Abel, B.

C.

Crosse, and

G.

V.

Hutson,

Chem.

and

Ind.,

1966, 238.

26s

J.

D.

Cotton,

J.

Duckworth,

S.

A.

R.

Knox,

P.

F.

Lindley,

I.

Paul,

F.

G.

A.

Stone, and

P.

Woodward,

Chem.

Comrn.,

1966, 253;

F.

Bonati,

S.

Cenini,

D.

Morelli,

and

R.

Ugo,

J.

Chem.

SOC.

(A),

1966, 1052.

266

(a)

R.

Ugo,

F.

Cariarti,

F.

Bonati,

S.

Cenini, and

D.

Morelli,

Ricerca

Sci., 1966,

86,

253;

(b)

G.

W.

Parshall,

J.

Amer. Chem.

Soc.,

1966,

88,

704.

267

(a)

A.

Mohammed and

D.

P.

N.

Satchell,

J.

Chem.

SOC.

(B),

1966, 527;

(b)

C.

C.

Addison and

W.

B. Simpson,

J.

Chem.

SOC.

(A),

1966, 776.

s6*

(a)

J.

P.

Clark

and

C.

J.

Wilkins,

J.

Chem.

SOC.

(A),

1966, 871;

(b)

F.

W.

B.

Einstein

and

33.

R.

Penfold,

Chem. Comm.,

1966,780.

269

C.

E.

Freidline

and

R. S.

Tobias,

Inorg.

Chern.,

1966,

6,

354.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

DOWNS,

EBSWORTH

AND

TURNER:

THE

TYPICAL

ELEMENTS

167

NO,-

in

solution,

in

contrast

to

the behaviour of Me,Sn2+. The formation

and properties

of

PbCl, and its derivatives have been re~iewed.27~

In

(Me3Pb),M

(M

=

P,

As)

the infrared spectra imply that the molecules are

pyramidal at M; the

Sb

derivatives could not be 0btained.~7l Triorganolead

borohydrides,272 made from R,PbOMe and

B2H6,

are liquid at

-30°,

and

decompose at room temperature

to

R6Pb2; with MeOH they give R3PbH at

-

78".

Exchange between R,SnH and R,Pb-imidazole derivatives has

been used to generate Pb hydrides

for

addition

in

situ

to

unsaturated

systems;273 addition of Pb-OR

274a

and Pb-N

274b

to multiple bonds has

been studied. The infrared spectra

of

R,Pb(SeCN) and Ph,Pb(SeCN),

indicate that the compounds do not contain Pb-N bonds.275

Nitrogen.

A

collection of reviews dealing with aspects of the inorganic

chemistry of

N

has been p~blished.~760 Several systems involving the

reaction of nitrogen gas with transition-metal ions have been reported.276b

The configuration at

N

in aniline

2770

and in dimethylaniline

277b

is non-

planar; the n.m.r. spectrum of (C3F7)2NOC,F7, made from (C,E',),NO and

C3F71, indicates slow inversion at

N.277c

The red adduct

277d

NH,I,NH, loses

NH3

under

a

vacuum at

-go",

and at

-70"

it

gives

NHI,.

A

review

of

inorganic nitrogen-iodine compounds has been p~blished.~77*

The salts (ClCH: NH2)+SbC1,- and (C12C:NH2)+SbC1,- react with water

or

alcohols

278

to substitute

OR

or

OH

for C1 bound to carbon. Reaction

between MeSCl

or

CF,SCl and [(CF3)2N]2Hg gives

27D0

(CF3),NSMe

or

(CP,),NSCF,

;

cyanogen chloride reacts with (CF,),NCl to produce

279b

(CF,),NN:CCl,, which forms

[(

CF,),NNCF,],Hg with

HgF2,

and (C3F8N2)2

with NaF. Irradiation

of

m,PF,

gives several radicals,280 among which

PF2

and

N2H,+

(formed from

NH,+)

were identified by e.s.r. Potassamide

and (Me,NNH,)+Cl- in liquid ammonia form Me,"€€, a hygroscopic,

explosive solid, most satisfactorily handled as its adduct with two molecules

of butanol, which gives Me,NNCN with

CCI,

and behaves as a strong base.281

The instability of the explosive N,H7SO4, produced from anhydrous

N2H4

270

J.

Szychlinski,

Wi&o8ci

Chem.,

1966,

20,495.

271

H.

Schuxnann,

A.

Roth,

0.

Stelzer,

and

M.

Schmidt,

Inorg.

Nuclear Chem. Letters,

272

E.

Amberger and

R.

Honigschmid-Grossich,

Chern. Ber.,

1966,

99,

1673.

275

H.

M.

J.

C.

Creemers,

A.

J.

Leusink,

J.

G.

Noltes,

and

G.

J.

M.

van der Kerk,

Tetrahedron Letters,

1966, 3167.

274

(a)

A.

G.

Davies and

R.

J.

Puddephatt,

J.

OrganometaUic Chem.,

1966,

5,

590;

(b)

W.

P.

Neurnann

and

K.

Kiihlein,

Tetrahedron Letters,

1966, 3415.

176

E.

E.

Aynsley,

N.

N.

Greenwood,

G.

Hunter, and

M.

J.

Sprague,

J.

Chem.

SOC.

(A),

1966,

1344.

276

(a)

"

Developments

in

Inorganic Nitrogen Chemistry,"

ed.

(1.

B.

Colburn,

Elsevier,

vol.

1,

1966;

(b)

M.

E.

Vol'pin and

V.

B. Shur,

Nature,

1966,

209,

1236;

K.

B.

Yatsimirskii and

V.

K.

Pavlova,

Doklady

Chem.,

1965,

165,

1088.

277

(a)

D.

G.

Lister and D.

G.

Tyler,

Chern. Comm.,

1966, 152;

(b)

L.

V.

Vilkov

and

T.

P.

Timasheva,

Doklady

Chenz.,

1965,

161,

261;

(c)

R.

E.

Banks,

M.

G.

Barlow,

R.

N.

Haszeldine, and

M.

K.

McCreath,

J.

Chem. SOC.,

1965, 7203;

(d)

J. Jander and

U.

Engel-

hmdt,

2.

anorg.

Chem.,

1966,

341,

146;

(e)

U.

Engelhardt and

J.

Jander,

Fwtschr.

Chem.

Forsch.,

1966, 5, 663.

278

E.

Allenstein and

A.

Schmidt,

2.

anorg. Chem.,

1966,

344,

113.

279

(a)

H.

J.

Emelbus and B.

W.

Tattershall,

J.

Inorg.

Nuclear Chem.,

1966,

28,

1823;

(b)

R.

C.

Dobbie and

H.

J.

EmelBus,

J.

Chem.

SOC.

(A),

1966, 933.

880

J.

K.

S.

Wan,

J.

R.

Morton,

and

H.

J.

Bernstein,

Canad.

J.

Chem.,

1966,

44,

1957.

181

R.

Appel,

H.

Heinen,

and

R.

Schollhorn,

Chm.

Ber.,

1966, 99,3118.

1966,

2,

311.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

168

INORGANIC CHEMISTRY

and

H3N+*S03-,

may imply that the compound

is

a derivative

of

triazine.28"

Salts of the substituted triazanium ion

282b

H2NNR2*NH2+, are obtained

from H2NCl and either

R,"H,

or

(CH,O),PNR,.

The adducts RN,,SbCl,

react with

R'C1 (R

=

Me or

H;

R

=

H

or

Me,C) at

-78"

to

give

adducts

282c

formulated as [RR'"N]+SbCl,-; the most thermally stable is

H,N,+SbCl,-, which loses N2 in boiling CH2C12. The thermal decomposition

of

M(N,),

(M

=

Crt,

Sr,

Ba)

in

some organic solvents gives

M&,

a

black

powder

283

which may contain

N4s-.

a planar molecule

with

non-equivalent

N

atoms (N-N

=

1-85

&

0.03

A);

the microwave spectrum

of

trans-HNO,

has been obtained

284b

from a mixture of NO, NO,, and

H20,

and the infrared spectra

of

both

cis-

and trans-forms in the vapour and solid

have been recorded.28k The hydrogen-bonded anions H(N02)2- and

H(N03),- have been obtained as salts

of

large cati0ns.~8~

The infrared

spectrum of

NO,AsF,,

together with X-ray powder data, suggests that the

compound may be

a

mixture

of

salts

of

the NO+ and NO2+

ions;286u

Raman

spectroscopy

288b

indicates that N,O, gives

NO2+

in SeO,.

Irradiation

of

NOCl

and

C2F4

gives (among other products)

(C1CF2CF,)2NON0,

from

which the relatively stable radical

(

C1CF2CE",),N0 has been obtained.287

Fluorination

of

H2NS(0),NMe2 at

30"

gives (with a little

MeNF,)

Me,NF,

an unstable liquid giving an equimolar adduct with

HC1

in

which the

N-I?

bond is apparently preserved.288a

A

simple way

of

preparing FNO

from

N204

and

KF

or CsF has been described.2s8b

The new compound

O",

has

been obtained by different methods;289

it

is

a strong oxidizing agent, and

gives

1

:

1

adducts with

MF,

(M

=

As

or

Sb) formulated as

P2NO+MF6-.

Heating

of

NF3,

F,,

and SbF, under pressure gives

Z9Oa

NF,+SbF,-, and the

action

of

a glow discharge on

NF,,

F,,

and

AsF,

at

-

78"

gives

29*b

NF4+AsF6-.

The solids decompose at

270"

(Ad?,-) orm.

300"

(SbF,-); the

As(v)

derivative

is

hygroscopic and readily hydrolysed, and its crystal structure resembles

that

of

PC14+PCl,-.

The chemistry

of

NF, has been re~iewed.2~1

Properties

of

NF

compounds

such as electron amties and ionisation potentials have been calculated

The microwave spectrum

of

N203

indicates

282

(a)

F.

Feh6r and

K.-H.

Linke,

2.

anorg.

Chm.,

1966,

344,

18;

(b)

K.

Utvary

and

H.

H.

Sisler,

Inorg.

Chem.,

1966,

5,

1835;

(c)

A.

Schmidt,

Chem. Ber.,

1966,

99,

2976.

28s

Y.

Okamoto and

J.

C.

Goswami,

Inorg.

Chem.,

1966,

5,

1281.

284

(a)

R.

L.

Kuczkowski,

J.

Amer.

Chem.

SOC.,

1965,

87,

5259;

(b)

A.

P.

Cox

and

R.

L.

Kuczkowski,

ibid.,

1966,

88,

5071;

(c)

G.

E.

McGraw,

D.

L.

Bernitt, and

I.

C.

Hisatsune,

J.

Chem.

Phys.,

1966,

45,

1392.

286

B. D.

Faithful and

D.

0.

Tuck,

Chem.

and

Ind.,

1966, 992;

B.

D.

Faithful,

R.

D.

Gillard,

D.

G. Tuck, and

R.

Ugo,

J.

Chem.

SOC.

(A),

1966, 1185.

286

(a)

S.

I.

Morrow

and

A.

R.

Young,

Inorg.

Nuclear

Chem. Letters,

1966,

2,

349;

(b)

G.

Kempe and

D.

Seifert,

2.

anorg.

Chem.,

1966,

348,

124.

287

W.

D.

Blackley,

J.

Awr.

Chem.

SOC.,

1966,

88,

480.

(a)

R.

A.

Wiesboeck and

J.

K.

Ruff,

Inorg.

Chem.,

1966,5,1629;

(b)

C.

T.

RrttclXe

and

J.

M.

Shreeve,

Chem.

Comm.,

1966, 674.

B89

N.

Bartlett,

J.

Passmore, and

F.

J.

Wells,

Ghem.

Comm.,

1966, 213;

W.

B.

Fox,

J.

S.

MacKenzie,

N.

Vanderkois,

B.

Sukornik,

C.

A.

Warnser,

J.

R.

Holmes,

R.

E.

Eibeck,

and

B. B.

Stewart,

J.

Amer.

Chem.

SOC.,

1966,

88,

2604.

890

(a)

W.

E.

Tolberg,

R.

T.

Rewick,

R.

S.

Stringham, and

M.

E.

Hill,

Inorg.

Nuclear

Chem. Lettera,

1966,

2,

79;

(b)

J.

P.

Guertin, K.

0.

Christe, and

A.

E.

Pavlath,

Inorg.

Chem.,

1966,

5,

1921.

291

C.

B.

Colburn,

Chem.

in

Britain,

1966,

2,

336.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

DOWNS,

EBSWORTH

AND

TURNER:

THE

TYPICAL

ELEMENTS

169

using Huckel LCAO-MO meth0ds.2~~~ The acid-catalysed exchange between

HNE,

and

D,O

has been investigated.292b

There was no evidence of

pro-

tonation of

IE",

by

a

variety of protonic acids;292c,

d

a,

1

:

1

complex is

apparently formed with AIMe, at

-78",

which loses

CH4

at that temperature,

but reaction with GaMe,

to

liberate

CH,

is

slow at

room

temperature.2920

Reactions of

RNF,

with organolithium reagents and with nitric acid have

been ~tudied,2~2~ and the hydrolyses of

NF,,

N2F4, and both

cis-

and

trans-

N,F2 investigated.

292f

Fluorination of buffered aqueous

H2NCIN

gives

N

N

zzc:

II

(26;

Z

=

F)

(27;

Z

=

RF)

Q-0

P

F2CN2,

identified spectroscopically

293a

as

F,NCN

rather than FNCNF; with

CsF

it

gives

(26).

The action of Pb(OAc), on (RF)2C=N*NH2

gives (R,),CNN and reaction between the same oxidizing agent and

(CF,)

,C-NE-NH gives

perfluorodimethyldiazirine

2936

(27). Mixtures

of

CO

and

N2F4

afford F,NCFO when irradiated.2ga Perfiuorohydrazine reacts

with CFBr, and related compounds

293d

to form

FN:

CFBr. Adducts

of

SbF,

(Sb

:

N

=

1

:

1)

with

N2F4

and with both

cis-

and trans-N,F, have been

obtained ;294 the

N2Fz

adducts give exclusively cis-N2F, on decomposition.

Spectroscopic evidence leads

to

the formulation of

N2F,,2SbF5

as

FzN"+Sb2Fll- and of N2F,,2SbF, as N2F+Sb2F11-. Fluorination of

NaN,

can be controlled

295

to

give either

trans

or

cis,trans

mixtures of

N2F2.

The

cation Me,C=N(Me)F+ is formed296 when ButNF, reacts with BF, or

H2S04

;

the fluorination

of

cyanuric chloride

297u or

of

297b

H2NC(

:NH)

S02H

gives

CF2(NF2),.

Phosphorus.

The structure

of

violet

P

is based on

Ps

groups (atoms as in

As,S,)

and

P,

groups, linked through further

P

atoms to give an infinite tube-

like struct~re.~~~~ Irradiation

of

PH,

in

a

Kr

matrix at

4°K

gives

298b

PH,,

but irradiation of

ASH,

gives only

As

and

H

atoms.

Reactions involving

292

(a)

J.

J.

Kaufman,

I;.

A.

Burnelle,

and

J.

R.

Hamann,

Adv.

Chem.

Ser.,

1966,

54,s;

(b)

W.

E.

Becker and

F.

J.

Impastato,

ibid.,

p.

132;

(c)

J. N.

Keith,

R.

J.

Douthart,

W.

K.

Sumida,

and

I.

J.

Solomon,

ibid.,

p.

141;

(d)

A.

D.

Craig,

G.

A.

Ward, C.

M.

Wright, and

J.

C.

W.

Chien,

ibid.,

p.

148;

(e)

H.

F.

Smith,

J.

A.

Castellano, and

D. D.

Perry,

ibid.,

p.

155;

(f)

G.

L.

Hurst and

S.

I.

Khayat,

ibid.,

p.

245.

293

(a)

M.

D.

Meyers

and

S.

Frank,

Inorg.

Chem.,

1966, 5, 1455;

(b)

D.

M.

Gale,

W.

J.

Middleton and

C.

G.

Krespan,

J.

Amer.

Chem.

SOC.,

1966,

88,

3617;

(c)

G.

W.

Fraser

and

J.

M.

Shreeve,

Inwg.

Chem.,

1965,

4,

1497;

(d)

D.

H.

Dybrig,

ibid.,

1966,

5,

1795.

I

I

a94

J.

K.

Ruff,

Imrg.

Chem.,

1966,

5,

1791.

2Qb

H.

W.

Roesky,

0.

Glemser,

and

D.

Bormann,

Chm.

Ber.,

1966,

99,

1589.

296

K.

Baum

and

H.

M.

Nelson,

J.

Amr.

Chem.

Soc.,

1966, 88,4459.

8*7

(a)

M.

A.

Englin,

S.

P.

Makaror,

S. S.

Dubov

and

A.

Ya.

Yakubovich,

J.

Gem.

Chem.

(U.X.S.R.),

1965,3!5,1419;

(b)

R.

J.

Koshar,

D.

R.

Husted, and

R.

A.

Meiklejohn,

J.

Org.

Chem.,

1966, 31,4232.

298

(a)

H.

Thurn

and

H.

Krebs,

Angew.

Ch.,

Internat. Edn.,

1966,5,1047;

(b)

R.

L.

Morehouse,

J.

J.

Christiansen, and

W.

Gordy,

J.

Chem.

Phys.,

1966,

45,

1747.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

170

INORQANIC

CHEMISTRY

apecies

in

which an unpaired electron

is

associated with

a

P

atom have been

reviewed.20Qa Alkali metals react with

phenylbiphenylenephosphine

in

THF

,Oob

(28),

as with triphenylphosphine,2Q9c to remove the phenyl group.

The anion formed reacts with more alkali metal, giving a radical-anion which

dimerizes through

P.

The importance

of

(Ipd)minteractions,

and

of

con-

jugation through

P,

has been discussed in relation

fo

the

U.V.

spectra

of

phenylphosphorane~,~OO~ of phosphine ylides,soob and

of

other species.3m

The structural chemistry

of

phosphorus compounds has been extensively

reviewed.801o In the crystal, the angle

301b

at

or-C

in

Ph3P=c----C=0

is

14!55".

The n.m.r. spectra of (p-tolyl),M

(M

=

P,

As,

Sb)

show a single Me-

proton resonance, indicating rapid positional exchange

;

in

spirophos-

phoranes

(29),

two Me-proton resonances are observed when

R

is

1-naphthyl

or

9-anthryl, implying that the

bulky

substituents slow the exchange.Wza

The bond angles at

P

in

PF,

and related species have been discussed

in

terms

of

electron-pair repulsions and delocalised molecular orbital

theory.302: The

n.m.r.

spectra of

MH3,

MH2-

(M

=

P,

As),

MeAsH,, and

MeAsH-

have been determined, and the relative acidities of the hydrides

estimated.

230

The mass spectra of the products of thermaI decomposition of

P2H4

or

the

hydrolysis

of

Ca3P2 have led to the postulation

303

of

a

number

of

ring and

chain derivatives, from

P2H2

and

P3H5

to

PI2H4

and

PI4H.

Hydrolysis

of

M3N2

mixed with

M3Z2

(M

=

Mg, Ca;

2

=

P,

As)

gives

Z3H5,

Z2NH4,

and

Me Me

S

R

-

-

PtBun3

s-

Me

Me

related species, identified by mass ~pectra.~04 In

DMF,

KPH,

and

P4

com-

bine

to

give

KP,H2,

formulated

305

as

containing

P,H,-.

Methanolysis

of

(CF3P),

gives H(

CF,P),H,

and the less stable

H(

CF3P),H

is

probably formed

from

(CF3P),

and n-dodecyl alcoho1;306 the reaction

of

MeP(NMe,), with

890

(a)

C.

Walling and

M.

S.

Pearson,

"

Topics

in

Phosphorus Chemistry,"

1966,

3,

1;

(b)

A.

D.

Britt and

E.

T. Kaiser,

J.

Org. Chem.,

1966,31,112;

(c)

A.

D. Britt and

E.

T.

Kaiser,

J.

Phys. Chem.,

1966,

69,

2775.

i+oo

(a)

J.

E.

Bissey and

H.

Goldwhite,

Tetrahedron Letters,

1966, 3247;

(b)

H.

Fischer

and

H.

Fischer,

Chem.

Ber.,

1966,

99,

658;

(c)

H.

Goetz

and

H.

Juds,

Annden,

1966,

098,

1.

*01

(a)

D.

E.

C.

Corbridge,

"

Topics

in

Phosphorus Chemistry,"

1966,

3,

57;

(b)

J.

J.

Daly

and P.

J.

Wheatley,

J.

Chem.

SOC.

(A),

1966, 1703.

(a)

D.

Hellwinkel,

Angew. Chem.,

Internat.

Edn.,

1966,

5,

726;

(b)

R.

J.

Cillespie,

Iwg. Chem.,

1966,

5,

1634;

(c)

L.

S.

Bartell,

Inorg. Chem.,

1966,

6,

1635.

SO8

M.

Baudler,

H.

Stiindeke,

M.

Borgardt, and H. Strabel,

Naturwiss.,

1965,

52,

345;

M.

Baudler,

H.

Stiindeke,

M.

Borgardt,

H.

Strabel, and

J.

Dobbers,

ibid.,

1966,

63,

106;

T.

P.

Fehlner,

J.

Amer. Chem.

SOC.,

1966,88, 1819, 2163.

SO5

F.

Knoll

and

G.

Bergerhoff,

Monatsh.,

1966, 97,

808.

808

A.

B.

Burg

and

L.

K.

Peterson,

Inorg.

Chem.,

1966,

5,

943.

P.

Royen and

C.

RocktBschel,

2.

anorg.

Chem.,

1966,

346,

290.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

DOWNS,

EBSWORTH

AND

TURNER:

THE

TYPICAL

ELEMENTS

171

HPPh, gives

307a

MeP(PPh,),, which reacts with

S,

forming MeP(PSPh,),;

it

is

concluded from the n.m.r. spectrum of (PhMe)PP(MePh) with

(2,4,6)-

trideuterio-phenyl groups that inversion

is

slow at

room

temperature

307*

but fast

at

180".

The molecular complexity

of

(PhP), in solution

is

confusing, perhaps

because the system

is

more labile than was once believed. In the solid, there

are pentameric (m.p.

149--50"),

hexameric, and more complex modifica-

ti0115.3070

The form of m.p.

149-50"

has a mol.

wt.

in

solution corres-

ponding initially to (PPh),, but the value drops with time in

HCBr,

or

even

on standing as solid at

-18".

The

31P

n.m.r. spectra of melts of (PhP),

contain peaks assigned

to

monomeric PhP, as well as to cyclic forms.308b

The action of alkali metals

M

on (PhP), m.p.

154-156"

dissolved in

THF

or

dioxan gives

MJPhP),,

sometimes solvated

(n

=

4,3,2,

depending on

M

and

conditions), formulated with linear

P-P

systems; with water, they give

H,

and (PhP), if

n

=

4,

the linear H(PPh),H being a presumed intermediate, but

if

n

=

2

or

3

hydrolysis involves

P-P

fissi0n.~08~ Under reflux, (PhP), (m.p.

154-156")

reacts

with

K

in

THE'

to

give red K,(PPh),, assigned a cyclic

structure because the

31P

n.m.r. spectrum indicates equivalent

P

atoms.308d

The mass spectra of mixtures

of

(MeP), and (EtP), that had previously been

distilled at

150"

showed species

30~

Et,Me,-,P,

(n

=

0-5);

the mass spec-

trum

of

(EtP), contained

s~~~

peaks due

to

(EtP),. The action

of

Hg

on

C,F,PX,

(X

=

Br,

I)

gives

310

(C,F,P),,

with

n

=

5

(mass spectra, mol.

wt.

in CH,Br,). The action

311

of

S

on

(CF3P),

gives (CF,P),S, which reacts with

Me,P to give Me3PS.

The compounds

PHF,

and PH,F3 have been obtained from

H,,P(O)(

OH),-,

(n

=

1

or

2)

in anhydrous

HF;

they are monomers as vapours, though there

is evidence that

PH,F,

is

associated (b.p.

3.8").

The n.m.r. spectra indicate

time-dependent exchange processes, but the infrared spectra are consistent

with equatorial H atoms in trigonal bipyramid~.~~~" The action

of

HI

on

Me2NPSF, gives

312b

SPF,H. The heat of formation of

PF,

by fluorine

bomb calorimetry is

313

dHf(298) (a-white

P)

PI?,

=

-380.3

&

0.3

kcal./

mole. The action

314a

of CuCN or Cu20 on

PF,I

(made

315

from F,PNMe,

and

HI)

gives F2PCN or

P,POPF,;

the action314a, of Hg

on

PF21

forms

PP,,

which gives

a

weak

e.s.r.

signal,314u perhaps due to

PF,.

The vibra-

tional spectra of

P,I,

in CS, indicate that the molecule has the

trans

(a)

L. Maier,

Helv. Chim. Acta,

1966,

49,

1119;

(b)

J. D.

Lambert and

D.

C.

Mueller,

J. Amer. Chem. Soc.,

1966,

88,

3669.

(a)

M.

Baudler, K. Kipker, and

H.-W.

Valpertz,

Natuwiss.,

1966,

53,

612;

(b)

E.

Fluck and K. Issleib,

2.

Naturforsch.,

1966,21b, 736;

(c)

K.

Issleib and K. Krech,

Chem. Ber.,

1966,

99,

1310;

(d)

K.

Issleib and

E.

Fluck,

Angew. Chem., Internat.

Edn.,

1966,

5,

687.

(a)

K. Schmidt, R. Schroer, and

H.

Achenbach,

Angew.

Chem.,

Internat.

Edn.,

1966,5, 316;

(b)

A.

H.

Cowley and

R.

P.

Pinnell,

Inorg. Chem.,

1966,

5,

1469.

A.

H.

Cowley and

R.

P. Pinnell,

J.

Amer. Chern. SOC.,

1966,

88,

4533.

sll

A.

B. Burg,

J.

Amer. Chem.

Soc.,

1966, 88,4298.

sla

(a)

R.

R.

Holmes

and

R.

N.

Storey,

Inorg.

Chem.,

1966,5,2146;

(b)

T.

L.

Charlton

and

R.

G.

Cavell,

Chem. Cmm.,

1966, 763.

sls

P.

A.

G.

O'Hare and

W.

N.

Hubbard,

Trans.

Farday

Soc.,

1966, 62,2709.

s14

(a)

R.

W.

Rudolph,

R.

C.

Taylor,

and

R.

W.

Parry,

J.

Amer.

Chem.

Soc.,

1966,

88,

3729;

(6)

M.

Lustig,

J.

K.

Ruff,

and

C.

B.

Colburn,

J. Amer. Chem.

SOC.,

1966,

88,

3876.

R.

W.

Rudolph,

J.

G.

Mom, and

R.

W.

Parry,

Inorg.

Chem.,

1966,5, 1464.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

172

INORGANIC

CHEMISTRY

configuration in solvents, as in the contrary to an earlier report

;

some

details

of

the vibrational and the n.m.r. spectra are consistent with the

equilibrium

Several phosphane oxides (from P,H,O to

P,H50),

the products of hydro-

lysis

of

Ca,P2, have been identified

from

their mass spectra.s17

A

number

of

reactions of P,O, have been investigated;S1g"

it

behaves as

a

quadridentate,

non-chelating ligand.31gb The formulae

of

various polyphosphites have been

deduced

S18c

from

the conductivities

of

solutions

of

phosphites of Rb and

Cs

in

aqueous

&PO,.

The reaction of

SO,

with

MsP3OlO

(M

=

Na,

K)

gives

P,05

and

S2072-

(Na)

or

S,O,,Z-(K);

heating

of

the products

of

the reaction with

the

Na

salt to their

m.p.

gave

SO,,

leaving sulphate-phosphate glasses.SIQO

Thermodynamic properties associated with ionisation

of

H3PO4, H4P20,,

and

H,P301,

have been determined,319b and the acidity functions

of

(X,Y)P(O)OH

in

DMSO

and ethylene glycol

(X,

Y

may be

PhO,

cyclohexyl,

H,OH, Ph, cyclohexyloxy) have been determined using primary aniline indi-

cator~.~l~c The reaction between

POBr,

and

FS0200S02F

follows the

equation

820a

POBr,

+

GFO,SOOSO,F

=

OP(OSO,F),

+

3Br(OS02F),

Phosphates have been shown cryoscopically and by conductivity to give

P(OH),f

in

H,SO,;

Ph,P

and (EtO),P are fully protonated, although

POP,

and POCl, behave as non-electrolytes.

320b

Sodium triphosphate and

fluoride ion react in water at

80"

to give

320c

(P,O,F)-, which degrades

slowly, forming

FP0,-,

FP,063-, and

P,074-.

The action

of

SPC1,

on

aqueous ammonia gives NH,+[POS(NH,),]-, which hydrolyses to

(NH,),[PO,S(NH,)] in the presence

of

acid;

3,1

in

20%

HF, the two

anions

give [POSF,]- and [PO,SF]2-, of which the former hydrolyses to the latter

in

HF-free aqueous acid. Passage of an electrodeless glow discharge through

a,

mixture of

PH,

and RSH

(R

=

H

or

Me)

gives (among other products)

H,PSR

(identified by

mass

spectra).322u

In

benzene,

(RPS,),

reacts

with Bun3P, giving crystals formulated as

(30);322b

the action

of

NaHX

(X

=

3P214

=

QP,

+

4P1,.

R

316

(a)

S.

G.

Frankiss,

F.

A.

Miller,

H.

Stammreich, and Th. Teizeira Sans,

Chem.

Comm.,

1966, 318;

(b)

R.

L.

Carroll and

A.

H.

Cowley,

ibid.,

p.

872.

317

M.

Baudler,

H.

Stfindeke,

J.

Dobbers,

M.

Borgardt, and

H.

Strabel,

Natzlwiss.,

1966,

53,

251.

318

(a)

J.

G.

Riess

and

J.

R.

van

Wazer,

Inorg. Chem.,

1966,

5,

178;

(b)

J.

G.

Riess

and

J.

R.

van Wazer,

J.

Amer.

Chem.

SOC.,

1966,

88,

2166;

(c)

M.

Ebert and

J.

Cipere,

CoEl.

Czech.

Chem.

Comm.,

1966,

31,

1.

319

(a)

S.

N.

Kondrat'ev and

S.

I.

Mel'nikova,

Rws.

J.

Inorg.

Chem.,

1966,

11,

429;

(b)

R.

R.

Irani and

T.

Taulli,

J.

Inorg. Nuclear

Chem.,

1966,

28,

1011;

(c)

A.

G.

Cook

and

G.

W.

Mason,

ibid.,

p.

2579.

320

(a)

D.

D.

Des

Marteau and

G.

H.

Cady,

Irwrg. Chem.,

1966,

5,

1829;

(b)

R.

J.

Gillespie,

R.

Kepoor and

E.

A.

Robinson,

Canad.

J.

Chem.,

1966,

44,

1203;

(c)

R.

E.

Mesmer,

J.

Inorg. Nuclear Chem.,

1966,

28,

691.

831

H.

H.

Falius,

Angew.

Chm.,

Internat.

Edn.,

1966,

5,

266.

323

(a)

P.

W.

Shenk and B. Leutner,

Angew. Chem., Internat. Edn.,

1966,

5,

898;

(b)

E.

Fluck and

H.

Binder,

ibid.,

p.

666.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

DOWNS,

EBSWORTH

AND

TURNER:

THE

TYPICAL

ELEMENTS

173

S

or Se) on Et,PSeCl gives salts

323a

of

(Et,PSeX),-; the species

RRR"P

react

with

KNCSe

to

give RRR"PSe, and R,P(Se)H has been

syn-

thesised from

R,PH

and red ~elenium.3~% The compound (Et,PSSe),

is

linked through Se and not through

S

in

the

The

reactions

of

organic P(m)-N compounds have been revie~ed.~~d

The very acidic (Ph,PS),NH is formed

325u

from Ph,P(S)NFI, and

Ph,P(S)Cl

;

methylation gives (Ph,PSMe),N+X-. The dimer (PhNPCl,),

reacts with liquid ammonia, producing a solid formulated

325b

as

[PhNHP(NH,),NP(NH,),NHPh]

+C1-.

The species obtained by the thermal

decomposition of

(

R,N) (RNH)P(

Z)NHR

(Z

=

0

or

S),

previously formulated

as monomers? give molecular weights in solution that correspond to dimers."a

The reaction

of

(CF,),NCI with

PF,

or

PF2C1

gives

327a

(CF3),NPF,C1

or

(CF,),NPF,Cl,

;

with (CF,),NCl and

M(CF,),,

the perfluoro-derivatives

[(CF,),N],M(CP,),-,

(n

=

1,2,

M

=

P,

As;

rt

=

3,

M

=

P)

are formed.

The reaction

with

Sb(CF,), is more c0mplex.~~7~ Dimeric (PhCC1:

N),

reacts

328

with

R,P- to give

[Ph(R,P)C:N],,

and with RP2- to give

(31).

The

chemistry

of

phosphonitrilic compounds has been revie~ed.3,~

In

(PNCl),, the variations in ionisation potential and in donor properties with

n

are interpreted in terms

of

modulation of the main, out-of-plane n-inter-

actions with in-plane

n'

Huckel-type interactions;330a the effects

of

side-

group repulsion on the relative thermal stabilities

of

PN

polymers has been

discussed.330b In the crystal, (MeNPCI,), contains a planar 4-membered

PN ring, the

P

atoms at the centres

of

trigonal bipyramids;331a the species

(RNPC13)2 react

331b

with

SO,,

giving (RNPOCl),, in which

C1

may be

replaced by

Z

(

=

SR,

NR,)

uisng Me,SiZ. Sulphamide and PCl, react

,N=P$lz

EtOzC,

,S,

,COzEt

N=PCI,

EtOzC

S

COlEt

02s

\

N

Me

,c=c\

/c=c,

(3

2)

(33)

(34)

[Reproduced

from

1%.

F.

Hawthorne and

R.

L.

Pilling,

J.

Amer.

Chem.

SOC.,

1966,

88,

3873.1

together to form

C1,P:

N*SO,*N:

PCI,,

which

with

ammonia gives the ring-

anion

(32),

and with (Me,Si),NMe the neutral compound

(33).331c

Many

derivatives

of

(PN), rings have been prepared, with substituents such as

a2s

(a)

W.

Kuchen and

B.

Knop,

Chem. Ber.,

1966,99,1663;

(b)

P.

Nicpon and

D.

W.

Meek,

Inorg. Chm., 1966,

5,

1297;

(c)

L.

Maier,

HeZv.

Chim.

Acta,

1966,

49,

1000;

(d)

S.

Husebye, Acta

Chem.

Scand.,

1966,

20,

51.

s24

R.

Burgada,

Ann.

Chim.

(France),

1966,

14,

15.

s26

(a)

A.

Schmidpeter and H.

Groeger,

2.

anorg. Chem.,

1966,

345,

106;

(b)

K.

Utvary,

V.

Gutmann,

and

Ch.

Kemenater,

Monatsh.,

1965,

96,

1751.

326

H.

Bock and

W.

Wiegriiber,

Chem.

Ber.,

1966,

99,

377.

s27

(a)

H.

J.

Emelkus

and

T.

Onak,

J.

Chem.

SOC.

(A),

1966, 1291;

(6)

H.-G.

Ang

and

H.

J.

EmelBus,

Chem.

Comm.,

1966, 460.

3a8

K.

Issleib and

A.

Balszuweit,

Chm.

Ber.,

1966, 99, 1316.

82s

T.

Yvornault and

G.

Casteignau,

Bull.

SOC.

chim.

France,

1966, 1469.

(a)

C.

E.

Brion,

D.

J.

Oldfield,

and

N.

L.

Paddock,

Chem.

Comm.,

1966, 226;

(b)

H.

R.

Allcock,

Inorg.

Chem.,

1966,

5,

1320.

831

(a)

L.

G.

Hoard

and

R.

A.

Jacobson,

J.

Chm.

Soc.

(A),

1966, 1203;

(b)

M.

Green,

R.

N.

Haszeldine, and G.

S.

A.

Hopkins,

&id.,

p.

1766;

(c)

M.

Becke-Goehring,

K.

Bayer,

and

T.

Mam,

2.

anorg.

Chem., 1966,

348,

143.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

174

INORGANIU

UHEMISTRY

ArNH

382a

or

RS,332b

and aromatic vic-dihydroxy-,

or

diamino-compounds,

or

dithiols, which give cyclised pr0ducts.33~~ Isomers have been identified,

usually by n.m.r., in mixed Ph-PhO, Ph-NMe,, and Ph-NHMe derivative~,~3~O

in mixed Me2N-OPh in mixed Me,N-NHPri species,s3& and in

mixed

Cl-NC5H1033Sd and

Cl-KKR

compounds.~3~ The formation and

basicities

of

some

of

these isomers has led to generalisations about the elec-

tronic structures and substitution reactions of the systems,38a,

C,

d,

6

and

a,

"

cis

''

effect has been proposed.333d The compound

(N,P,Ph,OH)

is

a

very

weak acid, perhaps because the anion

is

only slightly stabilized by

res~nance.~~~f

Of

the four geometric isomers of (PNPhCl),, three have been

identified

334a

by n.m.r.

;

the ring

in

(NPCI,)5

is very nearly planar.334b Pyri-

dine reacts with (PNCl,), to form an unstable solid

334e

P3N&l6py6, which

with water gives what may be

(PNpyOH),,

and ultimately

[PN(OH),],.

The chemistry of P-containing heterocyclic

CO~~OU~~S,~~~~

and of deriva-

tives

s358

of Ph,P and Ph5As, has been reviewed; the compounds Ph,PCl

and Ph,PC:PPh, give

336a

[(Ph,P),C*PPh,]+Cl- which reacts with excess

of

Me1

to

form

[

(Ph,P),C*PPh,MeJ2+21-. The compound described as

(Me,N),PCF, has been re-identified

336b

as (Me2N)3PF2. Ketones of the

general form RCOPR', have been prepared,,,& and their reactions studied

;

they are colourless when

R

is alkyl, but coloured when

R

is aryl. The direct

reaction under vigorous conditions between

P,

and

MeCl

or MeBr has been

used to make Me,PCl and Me4PBr in high yields.336d

A

number

of

new

(C,F,)P-derivatives has been prepared.337

Unlike Ph,N, Ph3M

(M

=

P,

As,

Sb) forms

1

:

1

adducts

338a

with C6Me6;

the compounds

of

composition Ph,PX

(X

=

Br,

I)

are apparently

338b

Ph,PHX, which react

with

I,

to

give Ph,PI, and

HI.

In

MeCN,

the species

Ph3MX2

(X

=

C1,

Br,

I)

behave as strong electrolytes

(M

=

P),

weak

electrolytes

(M

=

As),

or

non-electrolytes

(M

=

Sb,

Bi);

for

the

systems

Ph,PX, and X,

in

MeCN (X

=

Br

or

I),

conductometric titration indicates

that Ph3PX+ and

X3-

are formed.,,& The charge-transfer complexes

3s88

Ph3M,12

(M

=

N,

P,

As,

Sb) change with time to Ph,MI+I- when

M

=

P,

As.

*S3

(a)

H.

LederIe,

G.

Ottman and

E.

Kober,

Inorg. Chem.,

1966,

5,

1818;

(b)

A.

P.

Carroll

and

R.

A.

Shaw,

J.

Chem. SOC.

(A),

1966,914;

(c)

H.

R.

Allcock

and

R. L.

Kugel,

Inorg. Chem.,

1966,

5,

1016.

338

(a)

C.

T.

Ford,

J.

M.

Barr,

F.

E.

Dickson, and

I.

I.

Bezman,

Inorg.

Chm., 1966,

5,

351;

(b)

D.

Bell,

B.

W.

Fitzsimmons,

R.

Keat,

and

R.

A.

Shaw,

J.

Chem.

SOC.

(A),

1966, 1680;

(c)

S.

K.

Das,

R.

Keat,

R.

A.

Shaw, and

B.

C.

Smith,

ibid.,

p.

1677;

(d)

R.

Keat and

R.

A.

Shaw,

ibid.,

p.

908;

(e)

D.

Feakins,

W.

A.

Lart,

S.

N.

Nabi, and

R.

A.

Shaw,

ibid.,

p.

1831

;

(f)

C.

D.

Schmulbach and

V.

R.

Miller,

Inorg.

Chem.,

1966,5,1621.

884

(a)

B. Gmshkin,

A.

J.

Berlin,

J.

L.

McClanahan, and R.

0.

Rice,

Inorg. Chem.,

1966,

5,

172;

(b)

A.

W.

Schleuter and R.

A.

Jacobson,

J.

Amer. Chem.

SOC.,

1966, 88,

2051;

(c)

B.

I.

Stepanov and

G.

I.

Migachev,

J.

Qen. Chem.

fU.S.S.R.),

1965,

35,

2245;

(d)

H.

R.

Allcock,

R. L.

Kugel, and

K.

J.

Valany,

Inorg.

Chem.,

1966,

5,

1709.

385

(a)

G.

Miirkl,

Angew. Chem., Internat.

Edn.,

1965,

4,

1023;

(b)

G.

Wittig,

Bull.

SOC.

chim. France,

1966, 1162.

8*6

(a)

G.

H.

Binun

and

C.

N.

Matthewa,

J.

Arne?-.

Chem.

SOC.,

1966, 88,4198;

(b)

F.

Ramirez and

C.

P.

Smith,

Tetrahedron Letters,

1966, 3651;

(c)

K.

Issleib and

0.

LOW,

2.

anorg. Chem.,

1966,

346,

241;

(d)

L.

Maier,

Helv. Chim. Acta,

1966,

49,

2458.

537

H.

J.

Emelhus and

J.

M.

Miller,

J.

Inorg.

Nuclear

Chm.,

1966,

28,

662;

15.

Fild,

0.

Glemser, and

I.

Hollenberg,

Naturwiss.,

1966, 53, 130;

M.

Fild,

0.

Glemser, and

I.

Hollenberg,

2.

Naturforsch.,

1966,

21b,

920.

a**

(a)

R. A. Shaw,

B.

C.

Smith, and

C.

P.

Thakur,

Chem.

Comm.,

1966,228;

(b)

A.

D.

Bevoridge,

G. S.

Harris, and

D.

S.

Payne,

J.

Chem.

SOC.

(A),

1966,726;

(c)

A.

D.

Beveridge

G.

S.

Harris, and F. Inglis,

ibid.,

p.

520;

(d)

K.

R.

Bharhr,

S.

N. Bhat,

S.

Singh,

and

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

DOWNS,

EBSWORTH

AND

TURNER:

THE

TYPICAL

ELEMENTS

175

Solids

formulated on the basis

of

their spectroscopic properties and their

conductivities

in

acetone as (Ph,PPX,O)+X-

(X

=

C1,

Br)

are formed

338e

from

Ph,P and OPX,.

The addition compounds

of

the pentahalides

of

Group

V

have been

revie~ed.33~a Adducts

of

MeCN,

SO,,

and Me,N with

ME",

(M

=

P,

As,

or

Sb)

and

B35,2sbF,

are

described;

all

the MeCN and

Me,N

adducta except

&F5,

NMe, give conducting solutions

339b

in MeCN. The adduct Me,O,PF,

decomposes

34Oa

slowly at room temperature to Me,0+PF6- and

OPF,,

but

Me,S,PF, gives

PI?,,

Me,S+PF,-, and (Me,SSMe)+PF6-.

On

the basis

of

v.p. and related measurements,

it

is

concluded

3406

that

in

PF,,

ZMe,

(Z

=

0,

S,

Se) stability

is

in

the

order

0

-

S

>

Se.

Arsenic.

In

As

vapour

341

the tetrahedral

As4

has

d(As-As)

2.435

A.

There is evidence

342

from irreversible voltammigrams

of

millimolar

&(m)

and

As(v)

that

As(rv)

is

formed in

~*OM-HCIO,.

In crystalline MeAs(CN),,

as in As(CN),, the (AsCN) systems are apparently not linear.343Q

A

method

for

the preparation

of

pure As214

is

described;34sb the compound

is

thermally

stable at

150°,

and some

of

its physical and chemical properties have been

determined.34" The chemistry of organoarsenic compounds has been

reviewed.344 The reaction between Ph,AsH and

Et,M

(M

=

Mg

or

Zn)

gives

345Q

(Ph,As),M

or

(PhAsH),Zn

;

several substituted aminoarsoniurn

chlorides and cyclic

As-N

systems have been prepared by treating Ph&s

or

PhAsCl, with chloramine or mixtures

of

chloramine and ammonia ;345b

amines react

with

As(OMe),,

forming

345c

As-N

ring systems with Me0 groups

bound to

As;

the action

of

As(NMe,), on aldehydes

or

ketones leads

to

the

formation

345a

of

RRC(NMe,),.

Non-volatile solid oxyfluorides

ASOB',,

SbOF,,

and

SbO,F

have been prepared

346a

by

the thermal decomposition

of

the fluoride nitrates, themselves made

from

the fluoride chlorides and ClNO,.

A

compound

MeOAsF4,

formulated as [AsF,(OMe),

J

+AsF6

-,

is

produced

346b

by the action

of

MeOK on

&F5

in c&?~',c1,; it gives

a

conducting solution in

AsF,. The preparation of (CF,),As*NR*P(CF,),

[R

=

H,

Me,

P(CF,),]

from

(CF,),AsCl

and (CF3),PNHR

in

the presence

of

Me3N

(R

=

H,

Me)

or

from

[(CF,),P],NNa and

(CF,),AsCl

[R

=

P(CF,),J

has been described;346c

the As-N bonds are broken readily by HCl, though less

so

by BCl, and

BF,,

and

it

is deduced that (p4d)minteractions are weaker than are

(p3d)n-

C.

N.

R.

Rao,

J.

Inorg. Nuclear Chem.,

1966,

28,

1915;

(e)

E.

Lindner

and

H.

Schless,

Chem.

Ber.,

1966, 99, 3331.

839

(a)

M.

Webster,

Chem. Rev.,

1966,

66,

87;

(b)

I;.

Kolditz

and

W.

Rehak,

2.

anorg.

Chem.,

1966, 342, 32.

340

(a)

R.

A.

Goodrich

and

P.

M.

Treichel,

J.

Amer. Chem. SOC.,

1966,

88,

3509;

(b)

I.

K.

G.regor,

Austral.

J.

Chem.,

1966,

19,

1977.

841

Y.

Morino,

T.

Ukaji,

and

T.

Ito,

Bull.

Chem.

SOC.

Japan,

1966,

39,

64.

343

H.

A.

Catherino,

J.

Phys. Chem.,

1966,

70,

1378.

343

(a)

E.

0.

Schlemperer and

D.

Britton,

Aeta Cry&.,

1966,

20,

777;

(b)

M.

Baudler

and

H.-J.

Stassen,

2.

anorg. Chem.,

1966,

343,

244;

(c)

M.

Baudler

and

H.-J.

Stassen,

&id., 1966, 345, 182.

344

W.

R.

Cullen,

Adv. Organometallic Chem.,

1966,

4,

145.

84s

(a)

A.

Tzschach

and

H.

Hiickert,

2.

Chem.,

1966,

6,

265;

(b)

D.

Ham,

2.

anorg.

Chem.,

1966, 347, 123;

(c)

H.

Weingarten and

W.

A.

White,

J.

Org. Chem.,

1966,

31,

4041;

(d)

H.

Weingarten end

N.

A.

White,

J.

Org.

Chem.,

1966,

31,

4041.

348

(a)

L.

Kolditz and

E.

Rosel,

2.

anorg.

Chem., 1965,

341,

88;

(a)

L.

Kolditz

and

E.

Rosel,

I;.

anorg. Chczm.,

1965,

341,

88;

(c)

J.

Singh

and

A.

B.

Burg,

J.

Amer. Chem.

SOC.,

1966,

88,

718.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

176

INOBGANIO

CHEMISTRY

interactions. The action of

Hg

on

CF3AsI,

gives

347a

(CF,As),,

and possibly

(CF,As),

;

CF3COC1 reacts with Me4As2, forming

,478

Me,AsCOCF, and

Me,AsCl. The arrangement

of

the four

0

atoms round

As

in

the crystal

of

K[As(C,H402),] could be regarded

as

based on a trigonal bipyramid, with

a

stereochemically active lone-pair.348

The crystal structures

of

the salts M,SbX,

(M

is

Rb+,

Cs+,

or

NH4+;

X

is

C1 or Br), which formally contain Sb(rv), show the

presence of Sb(m) and Sb(v)

;

the Sb(v)Br,-octahedra are distorted, but

the Sb(m)Br,-octahedra are The stereochemistry

35*

of

Sb(v) has

been reviewed; solid SbC14F

is

tetrameric, with octahedral Sb and

F

bridges

(L

SbFSb

=

173"),

the Sb-F

ring

being slightly pu~kered.S~~~ The

vibrational spectra

of

Me,Sb have been assigned

S5lb

on the basis

of

a trigonal

bipyramid round Sb. The n.m.r. spectra

of

solutions

of

pairs of the

compounds Me3SbX2

(X

=

I?,

C1,

Br,

I)

in

CHCI,

show

352~

the presence of

mixed species at

-32";

exchange becomes rapid on the n.m.r. timescale at

temperatures between

7O0(Br/I)

and 150°(F/C1). The infrared spectra of

crystalline Me,SbX,

(X,

=

F-,

NO,-,

CO,2-,

SO4,-,

Cr042-,

C2042-)

indicate

352b

that these compounds are molecular in the solid; attempts

to

prepare Me,Sb2+(BF4),-

or

Me,Sb2f(SbE',)2- gave impure products and

Me,SbF,. The

lH

and

19F

n.m.r. spectra and the conductivities of solutions

of

SbF, in

HF

are interpreted

in

terms of the formation

of

species

H,F+

and

(SbnF5n+l)-; the abnormally high mobility of the

H,F+

ion indicates

a

proton transfer me~hanism.~~s

In

HF,

SbP40S0,F solvolyses

353

to

give

SbF,- and HS0,F. The thermodynamics associated with solvation equi-

libria between SbCI, and

a

number of donor solvents have been investigated

spectrophotometrically and calorimetrically.354

Azo-compounds such as

PhNNPh form complexes with SbCl,, SbCl,, and BiCI,.

Bismuth.

There

is

spectrophotometric evidence

356

to suggest the for-

mation

of

Bi+, Bi,3+ and

a

further associated species

in

solutions of Bi and

BiCl, in melts

of

NaCI/AlCI,

or

KCl/ZnCl,. The crystal structure

of

Bi(

H20),(N03)3

has been determined.

357a

The vibrational spectra

of

hydro-

lysed Bi(rn) perchlorate indicate that there

is

no change in the structure

of

the

cation

on

going from the solid to solution, and the frequencies have been

interpreted

S67b

in

terms

of

the octahedral cage complex cation, Big(OH2)B6+.

Formation constants for the mixed complexes [Bi(SCN),Br]S- and

847

(a)

A.

H.

Cowley,

A.

€3.

Burg,

and

W.

R.

Cullen,

J.

Amer. Chem. SOC.,

1966,

88,

3118;

(b)

W.

R. Cullen and

G.

E.

Styan,

Canad.

J.

Chm.,

1966,

44,

1225.

348A.

C.

Skapski,

Chem.

Comm.,

1966,

10.

349

S.

A.

Lawton

and

R.

A.

Jacobson,

Inorg. Chem.,

1966,

5,

743.

850

G.

0.

Doak

and

G.

0.

Long,

Trans. New York

Acad.

Sci.,

1966, 28,

402.

351

(a)

EL

Priess,

2.

Chem.,

1966,

6,

350;

(b)

A. J.

Downs,

R.

Schmutzler, and

I.

A.

352

(a)

G.

G.

Long,

C.

G. Moreland,

G.

0.

Doak, and

M.

Miller,

Inorg.

Chem.,

1966,

853

R.

J.

Gillespie

asld

K.

C.

MOSS,

J.

Chem.

SOC.

(A),

1966, 1170.

354

V.

Gutmann,

A.

Steininger,

and

E.

Wychera,

Monatsh.,

1966, 97,460.

855

L.

A.

Kazitsyna,

N.

B.

Kupletskaya,

V.

A.

Ptitsyna,

M.

N.

Bochkareva,

and

356

N.

J.

Bierrum,

C.

R. Boston,

G.

P.

Smith, and

H.

L.

Davis,

Inorg.

NucZear

Ch.

Antimony.

Steer,

Chem.

Corn.,

1966, 221.

5,

1358;

(b)

H.

C.

Clark

and

R.

G. Goel,

ibid.,

p.

998.

0.

A.

Rentov,

Rztss.

J.

Org. Chem.,

1966,

2,

567,570.

Letters,

1965,

i,

141.-

690;

(b)

V.

A.

Maroni

and

T.

G.

Spiro,

J.

Amer. Chem.

SOC.,

1966,

88,

1410.

357

(a)

P.

Herpin

and

K.

Sudarsanen,

Bull.

SOC.

France, MineraE

Grist.,

1965,

88,

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

DOWNS, EBSWORTH AND

TURNER:

THE TYPICAL ELEMENTS

177

[Bi(SCN),Br3l3- have been determined.358 The action of AgClO, on Ph,BiCl,

at room temperature leads

859a

to the formation

of

Ph4Bi+C10,-; treatment

of Ph,BiBr with pyridine gives

359b

Ph,Bi and PhBiBr2,2py.

Group

VI.-Oxygelz.

The magnetic susceptibility

of

02+

has been deter-

mined

360

from measurements with

o,+PtF6-

and

NO+PfP6-.

Oxygen

isotope exchange reactions of organic compounds have been reviewed.s61

The reactions

of

Lewis acids with MeO-

in

MeOH have been investigated

conductometrically, and several new derivatives have been prepared.36a

The chemistry of dissociated water vapour and related systems has been

a study of the products of an electrodeless discharge on

mix-

tures

of

H

atoms and

H,O,

vapour at low pressures does not support the

suggestion that metastable intermediates

(e.g.,

H204)

are formed.

36sb

The

thermal stability

of

inorganic peroxy-compounds has been considered,

364a

and the chemistry of organometallic and organometalloid peroxides re-

viewed.s64b The photolysis of

C,F20,

gives

CF(0)O

radicals, thus con-

fbming

364c

the suggested structure of the parent compound,

FC(O)*O,-C(0)F

;

this,

when photolysed with

SO,,

gives FC(0)OSOaF. The material

for-

mulated

365a

as But,O,, formed by the action of Ph3PC1,

on

a

mixture of

Ph,PO and ButOOH at

-78",

has

been described

3+35b

from its physical

properties as Me,C( OOBut),.

An

improved preparation

of

04F2,s66a preparations

of

05Fz

and

06F2,366b

and preparation

of

OaF2 from

OF,

and

0,

366c

have been given.

For

OF,,

AH,"(

-4*06&

2-20 kcal.mole-1) has been redetermined.367a From the

mass spectra

of

0,F2,

03F2, and

O,F,,

it is deduced that

0,F2

and

04F,

do

not exist

in

the vapour phase,367b and the bond dissociation energies

in

O,F,

have been estimated [D(FO-OF)

=

135;

D(F-OOF)

-

18

kcal./mole].

The radical

02F

s6sa

is

detected by 8.s.r.

in

photolysed liquid

OF2,368b

in

02F2,368c,

03F2,36& and

04F2,s6gS

and by infrared spectroscopy on photo-

lysis

of

On,

mixtures

in

matrices

at

low temperatures;36*f the radical OF

s58

E.

Josefowicz and

R.

Ladzinska-Kulinska,

Roczniki

Chem.,

1966,

40,

1615.

s6s

(a)

G.

0.

Doak,

G.

G.

Long,

S.

K.

Kakar, and L.

D.

Freedman,

J.

Amer.

Chem.

SOC.,

1966, 88,2342;

(b)

R.

Okawara,

K.

Yasuda and

M.

Inoue,

BuU.

Chem.

SOC.

Japan,

1966,

39,

1823.

s60

N.

Bartlett and

I.

P.

Beaton,

Chem.

Comm.,

1966, 167.

361

D.

Samuel and

B.

L.

Silver,

Adv. Phys.

Org.

Chem.,

1965,

3,

123.

s8s

(a)

M.

Venugopalan and

R.

A. Jones,

Chem.

Rev.,

1966,

66,

133;

(b)

N.

Hata and

P.

A.

Gigukre,

Canad.

J.

Chem.,

1966,

44,

869.

s64

(a)

I. I.

Vol'nov,

Russ.

Chem. Rev.,

1965,

36,

908;

(b)

G.

Sosnovsky and

J.

H.

Brown,

Chem. Rev.,

1966,

66,

529;

(c)

W.

B.

FoxandG. Franz,

Inorg.

Chem.,

1966,5,946.

366

(a)

N.

A.

Milas

and F.

G.

Arzoumanidis,

Chem.

and Ind.,

1966, 66;

(b)

R.

D.

Youssefyeh and

R.

W.

Murray,

ibid.,

p.

1531.

3e6

(a)

A.

G.

Streng,

Canad.

J.

Chem.,

1966,

44,

1476;

(b)

A.

G.

Streng and

A.

V.

Grosse,

J.

Amer.

Chem.

SOC.,

1966,

88,

169;

(c)

A.

G.

Streng and

L.

V.

Streng,

Imrg.

Nuclear

Chem. Letters,

1966,

2,

107.

867

(a)

W.

R.

Bisbee,

J.

V. Hamilton, R. Rushworth,

T.

J.

Houser, and

J.

M.

Gerhauser, Adv. Chem.

Ser.,

1966,54,215;

(b)

T.

J.

Malone and

H.

A.

McGee,

J.

Phya.

Chem.,

1965,

69,

4338;

T.

J.

Malone and

H.

A.

McGee,

ibid.,

1966,

70,

316.

868

(a)

R.

W. Fessenden and

R.

H.

Schuler,

J.

Chem. Phys.,

1965,

43,

2704;

R.

W.

Fessenden and

R.

H.

Schuler,

ibid.,

1966,44,434;

(b)

F.

I.

Metz,

F.

E.

Welsh, and

W.

B.

Rose,

Adv. Chem.

Ser.,

1966,54,202;

(c)

P.

H.

Kmai and A.

D.

Kirshenbaum,

J.

Amer.

Chem.

Soc.,

1965,87, 3069;

(d)

F.

E.

Welsh, F.

I.

Metz, and

W.

B.

Rose,

J.

Mol.

Spectro-

scopy,

1966,

21,

249;

(e)

A.

D.

Kirshenbaum and

A.

G.

Streng,

J.

Am.

Chem.

Soc.,

1966,

88,

2434;

(f)

A.

Arkell,

ibid.,

1965,

87,

4057;

R.

D.

Spratley,

J.

J.

Turner,

and

G.

C. Pimentel,

J.

Chem.

Phys.,

1966, 44, 2063.

C.

J.

Ludman and

T.

C.

Waddington,

J.

Chem.

SOC.

(A),

1966, 1816.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

178

INORGANIC

CHEMISTRY

has been detected by infrared spectroscopy

36Qa

on photolysis of

OF,

in

noble gas matrices at

4OK

but the e.8.r. detection

3139~

of

03'

on

photolysis

of

OF2

in CC13F at

77°K

has been questioned

888d

and the resonance reassigned

to

0,F.

The

lDI?

chemical

shift

in

O,F,

is

at unusually low field~;~70 the

bonding in

this

molecule and

in

related species containing

02-

or

NO-groups

has been described

s71

in terms

of

electron donation from the ligand

to

the

0,

(or

NO)

antibonding n-orbitals. Ketones

(X,Y)C=O

react quantitatively

with

F,

in

the presence of

MI?

(X,

Y

=

RF

or

F;

M

=

K,

Rb,

or

Cs)

at

-78"

to give

372u

(X,Y)CFOF;

the previously reported preparation

374b

by

fluorination of partially fluorinated alcohols gives low yields.

The properties

of

HCIOc

have been reviewed;373 the structure

of

C&O,

has

been determined by electron diffraction

;*y4

U.V.

spectroscopy indicates that

the complex between

(30,-

and ClO,

is

stronger

376

than that between C102-

and

UOZ2+.

Salts

NaXO,F,

(X

=

C1 or Br) are obtained

378

on

dissolving

NaXO, in cold

40%

HF.

Sutphur.

Further theoretical studies

of

the d-orbitals

of

S

have been

made;377a the relationship between chemical binding and

X-ray

spectra

of

S

compounds has been discussed.

87

7b

Ultraviolet and vibrational spectra of

R,S,

have been used in a theoretical analysis

of

the bonding in these com-

pound~;~~~~ the ultraviolet spectra

of

aromatic S-derivatives,378b and the

n.m.r. spectra

of

S

ylids

378e

and

of

ap-unsaturated sulphonium ~alts,s~~~ have

been discussed

in

relation to possible d-orbital participation

;

the e.8.r.

spectra

of

the radical-anions

of

diphenyl sulphone and di-p-tolyl sulphone

indicate strong ring interactions, perhaps through d-orbitals of

sulphur.87*

The reactions

of

atomic

S

have been reviewed,~7@~ and dissociation energies

of

diatomic molecules of the elements

S-Te

collected.379b From the n.m.r.

spectra

of

some ring compounds

of

S

and

Pt,

it

is deduced that inversion at

S

is slow;

880a

evidence has been presented to indicate that racemisation of

ButEtMeS +C1- involves inversion and

is

independent

of

heter0lysis.380~

Elemental forms of

S

containing

S,

and

S,,

units have been described;SBl*

a

review has been published

of

the synthetic use

of

the reactions between

86B

(a)

A.

Arkell,

R. R.

Reinhard,

and

L.

P.

Larson,

J.

Amer.

Chern.

Soc.,

1965,

87,

1016;

(b)

F.

Neumayer

and

N.

Vanderkooi,

Inorg.

Chem.,

1965,

4,

1234.

37*

N.

J.

Lawrence,

J.

S.

Ogden, and

J.

J.

Turner,

Chem.

Cmm.,

1966,

102.

871

R.

D.

Spratley and

G.

C.

Pimentel,

J.

Amer. Cham.

SOC.,

1966,

88,

2394.

s78

(a)

J.

K.

Ruff,

A.

R.

Pitochelli, and

M.

Lustig,

J.

Amer. Chem.

SOC.,

1966,

88,

873

G.

S.

Pearson,

Adu.

Inorg.

Chm. Radiochem.,

1966,

8,

178.

874

B.

Beagley,

Tram. Paraday

Soc.,

1966,

61,

1821.

876

C.

Gordon and

F.

Emmenegger,

Inorg.

Nuclear Chem. Letters,

1966,

2,

395.

877

(a)

C.

L.

Bendazzoli and

C.

Zauli,

J.

Ch.

SOC.,

1965, 6827;

D.

P.

Crag

and

T.

Thirunamachandrm,

J.

Chern. Phys.,

1966,

45,

3355;

(b)

D.

W.

Wilbur,

U.8.

Atomic

Energy

Comm.,

1966, UCRL-14379.

(a)

S.

D.

Thompson,

D.

(3.

Carroll,

F.

Watson,

M.

O'DonnelI,

and

S.

P.

McGlynn,

J.

Chem. Phys.,

1966,

45,

1367;

(b)

L.

Goodman

and

R.

W. Taft,

J.

Amer.

Chem.

SOC.,

1966,

87,

4385;

(c)

K.

W.

Ratts,

Tetrahedron Letters,

1966, 4707;

(d)

M.

C.

Caserio,

R.

E.

Pratt, and

R.

J.

Holland,

J.

Amer.

Chem.

SOC.,

1966,

88,

5747;

(e)

E.

T.

Kaiser,

M.

M.

Urberg, and

D.

H.

Eargle,

ibid.,

p.

1037.

878

(a)

H.

E.

Gunning,

Elem.

&u@hur,

Cham.

Phys.,

1965, 265;

(b)

J.

Drowart

and

P.

Goldfinger,

Quart.

Rev.,

1966,

20,

646.

880

(a)

E.

W.

Abel,

R.

P.

Bush,

P.

J.

Hopton,

and

C.

R.

Jenkins,

Chem.

Comm.,

1966,

58;

(b)

D.

Darwish and

G.

Tourigny,

J.

Amer.

Chem.

SOC.,

1966, 88,4303.

881

(a)

M.

Schmidt,

Elem.

Sulphur, Chern. Phys.,

1965, 327;

(b)

H.

Schumann

and

4531;

(b)

J.

H.

Prages

and

P.

G.

Thompson,

ibid.,

1965,

87,

230.

GF.

Mitra,

2.

anorg.

Chem.,

1965,

540,

110.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

DOWNS,

EBSWORTH

AND

TURNER: THE TYPICAL

ELEMENTS

179

elementary

S,

Se,

or

Te and R,MLi

(M

=

Si,

Ge,

Sn,

or Pb).381b Acid-base

concepts

in

the solvent liquid

S

have been discus~ed,38~~ and the solubilities

of

CS2

and of

SO,

3818

determined; the infrared

381f

and n.m.r.384

spectra

of

H2S

in liquid

S

suggest that an equilibrium between

H2S,

S

and

H2S,

is set up. The action of Na or

K

atoms

on

H2S

at

77°K

gives

s82a

H

2

S-.

Salts

R4N+SH-

have been obtained

S82b

from their strongly conducting

solutions

in

liquid

H,S;

H2S

is

weakly bound to the anions, the hydrogen-

bond energy being estimated as

ca.

5

kcal./mole,ss2b and as

>

7

kca1./mo1e,Sg2c by different workers.

Anions

BX,SH-

(X

=

F,

Cl,

Br,

Et),

(SiF4)2S2-, GeF4(SH),,-, SiC14S2-, and SiC14(SH)2- have been prepared

in

the

same sol~ent,3~~~, though the reaction with

B2Hs

was more complicated.

Exchange

382f

of labelled

S

between solvent

H2S

and

S,

CS2,

Me,S,

or

EtSH

is

slow

in

neutral solution;

in

the presence

of

Me3N, exchange

is

fast with

As,S,,

&2s,,

Sb,S,,

CS,,

and

S,

moderately fast with

P2s,,

and very slow

with

EtSH.

Dilution shifts

in

the n.m.r. spectra

of

RSH

in

CCl,

and other

solvents have been interpreted in terms

of

an

equilibrium between

mono-

mers and dimers, and the equilibrium constants calculated; indications

of

the formation

of

(PhSH),

in

CCl, are put down to changes

in

solution aniso-

tropy with concentrati~n.~~~~ The rate and products

of

autosidation of

dilute, aqueous, acidic sulphide

or

polysulphide solutions depend

s823(

on

the

concentration of

HS-.

A

method

for

the large-scale synthesis of

S,Cl,

(x

=3-6)

from

H2S,

(y

=

1-4)

and

SzC12

(z

=

1-2)

has been described.883

Correlations between the

(S4)

bond distance and the activation energy

for

displacement reactions by nucleophile~,~84~ and between the

(S-S)

dis-

tance and the dihedral 5~ngle,38~~ have been remarked. Alkali metal

fluorides react with SCF,

to

give F3CSC(S)F

and

(CF,S),CS, and the forma-

tion

of

SCF,-

was not detected;s855 oxidation

385b

of

MeSCF, with

HNOs

or

with

H202

in acetic acid gives MeS(O)CF,. The peduorothioketen

(CF,),C=C=S

has been obtained

386

by heating the dimer produced by the

S

RNH~

'

C

*SMe

$4

N-N

+

Me,/---,

Me

Me

Me,+

+/Me

S

-

CH2

-.

S

,

;S

-

CHI

-

s:

Mk

Me Me

(3

5)

(36)

(3

7)

M.

Schmidt,

Angew.

Chem.,

Inkmat. Edn.,

1965,

8,

1007;

(c)

T.

K.

Wiewiorowski

md

F.

J.

Touro,

J.

Phya.

Ch.,

1966,

'70,

3528;

(d)

F.

J.

Touro

and

T. K.

Wiewiorowski,

ibid.,

p.

3531;

(e)

F.

J.

Touro

and

T. K.

Wiewiorowski,

dbid.,

p.

3534;

(f)

T.

I(.

Wiewio-

rowski

and

F.

J.

TODO,

ibid.,

p.

234;

(g)

J.

B.

Hyne,

E.

Muller,

and

T.

I(.

Wiewioromki,

ibid.,

p.

3733.

(a)

J.

E.

Bennett,

€3.

Mile, and

A.

Thomas,

Chem.

Cm.,

1966, 182;

(6)

J.

D.

Cotton and

T.

C.

Waddington,

J.

Chem.

SOC.

(A),

1966,

785;

(c)

D.

H.

McDaniel

and

W.

G.

Evans,

Inwg.

Cbm.,

1966,

6,

2180;

(d)

J.

D.

Cotton and

T.

C. Waddington,

J.

Ch.

SOC. (A),

1966, 789;

(e)

J.

D.

Cotton and

T.

C.

Waddington,

ibid.,

p.

793;

(f)

J.

R.

Mickelsen,

T.

H.

Norris,

and

R.

C. Smith,

Inorg.

Chern.,

1966,

5,

911;

(9)

8.

H.

Marcus and

S.

I.

Miller,

J.

Amer.

Chem.

SOC.,

1966,88,3719;

(h)

J.

W.

Bowem,

M.

J.

A.

Fuller,

and

J.

E.

Packer,

Cbm.

and Ind.,

1966, 65.

(b)

A.

Hordvik,

Acta

Chem.

Scad.,

1966,

20,

1885.

(a) A.

Haw and

W.

Klug,

Angsw.

Chem.,

Internat. Edn.,

1966,

5,

845;

(b)

L.

M.

Yagupol'akii and

A.-G.

Panteleimonov,

J.

Qen.

Chm.

(U.S.S.R.),

1965,

35,

1123.

M.

S.

Rmsh,

Chm.

Comna.,

1966,

577.

383

F.

Fehhr,

J.

Grobell, and

F.

R.

Minz,

2.

anorg.

Chem.,

1966,

343,

146.

m4

(a)

R.

E.

Davis,

J.

B.

Lonis,

and

A.

Cohen,

J.

Amer.

Chem.

SOC.,

1966,

88,

1

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

180

INORQANIC

CHEMISTRY

action

of

SF,

and

HF

on (34). The reaction between Me,0+BF4-

and

(MeS),CH, gives

s87a

the bis(fluoroborate) of (35), and

this

when treated with

KOH

in

MeOH gives the fluoroborate of

(36).

A

compound formulated from

chemical and spectroscopic evidence

887b

as MeS0,CH: S0,NMe3 has been

obtained from the reaction between Me3N and MeS0,Cl in MeCN at

-40'.

The

vapours

of

CS,

and

SO,

do not react below

400",

but

in

the condensed

phase the ultimate product of reaction

is

polymeric material containing

S

chains with

CS

and

CO

groups.388

A

new

MO

description of the N4S4 molecule indicates that the role

of

the

d-orbitals

of

S

is

significant but not large, and predicts the formation

of

miom

N4SP-

(fi

=

1-4)

with delocalised n-electrons.389 The infrared

spectrum

of

SP,

is

consistent with symmetry (planar

ring),

though

CZb

symmetry (puckered ring) cannot be excl~ded.~~O The crystal symmetry

of

S,NH has been determined.391 The Gst product

of

the action

of

S,C1,

on

NH,

has been identsed

392

as monomeric NSCl. The free acid

H(H,NCS,)

has been obtained

393

from the ammonium salt and conc.

HCl

at

0".

The

molecules (NSC1)3394a and a-(NSOCI),Sg4b in the crystal are both

in

the chair

form,

with axial C1 atoms; crystalline S,N,Cl, consists

s94c

of puckered

S,N,Cl+ rings and

C1-

ions. The action

of

RC(:NOH)Cl

on

H,N*NH-CS2Me

gives

s9s

(37).

The chemistry

of

the compounds formed by

S4N4

with metals

has

been reviewed.396 The structure

of

the compound C,H,N,S, formed

from Me,S and H,NCl, has been reassigned

397

as Me,S(NH), rather than

Me2SNH+*NH-,

from

its

mass spectrum and reactions; with

Br,,

Me,S(N€I)NBr

is

produced, with gives [HNSMe,*NPPh,]+Br- with PPh,.

When AgF and

S

are heated to

140°,

blue SF,

is

f~rmed;~~g the compound,

characterised by analysis, is volatile at

-78"

in

vmuo,

reacts quantitatively

with

HI

to give iodine, and with

KBr

forms

SBr,.

In

acetone,

SCl,

reacts

with AgNO, or

KI

to form CISNO,

or

CISI; with excess of AgNO,, the un-

stable

S(N03),

may be formed. The conductometric behaviour

of

the solu-

tions

implies ionisation

of

the

S

cornpound~.~9~~

In

the absence

of

base,

C5Hl,,NSCl reacts

399b

with

(A

=

EtO, 4-Me2NC,H4, 4-Mec,H4s) to give

A@,

but

in

the presence of pyridine reaction with AH

(A

=

EtO, 4-MeC,H4S)

gives

C,H1PSA,

decomposed by acid.

The angle at

S

in crystalline

S(CN),

is

95.6',

and the (SCN) groups are (within error) linear.399e At

160"

and low

887

(a)

C.

P.

Lillya

and P.

Miller,

J.

Amer.

Chm.

SOC.,

1966,

88,

1669, 1560;

(b)

Q.

Opitz,

&I.

Kleeman,

D.

Biicher,

G.

Walz,

and

K.

Rieth,

Angew.

Chern.,

Int9lrzat.

Edn.,

1966,

5,

694;

G.

Opitz

and

D.

Bucher,

Tetrahedron Letters,

1966, 6263.

R.

Steudel,

2.

anorg.

Chmn.,

1966,

346,

265.

a*0

A.

G.

Turner

and

F.

S.

Mortimer,

Inorg.

Chm.,

1966,

5,

906.

J.

R.

N.

Warn

and

D.

Chapman,

Spectrochim.

Acta,

1966,

22,

1371.

aO1

EL

Garcia,

Cmpt.

rend,

Ser.

C.,

1966,

283,

1362.

M.

Becke-Goehring

and

D.

Schliifer,

2.

Naturforsch.,

1966,

21b,

492.

898

#.

#attow

and

V.

Hahnkamm,

Angew.

Chem.,

Inhmat.

Edn.,

1966,6,

316.

m4

(a)

G.

A.

Wiegers

and

A.

Vos,

Acta

Cryst., 1966,

20,

192; (b)

A.

C.

HazeU,

0.

A.

Wiegers,

and

A.

Vos,

{bid.,

p.

186;

(c)

A.

Zalkin,

T.

E.

Hopkins,

and

D. H.

Templeton,

Inwg.

Ch.,

1966, 5,1767.

806

A.

Dornow

and

K.

Fischer,

Chem.

Ber.,

1966,

99,

72.

1106

J.

Weiss,

Forhchr.

Ch.

Porsch.,

1966, 5, 635.

897

R.

Appel,

H.

W.

Fehlhaber,

D.

Hiinssgen,

and

R.

Schollhorn,

Chem.

Ber.,

1966,

888

D.

K.

Padma and

S.

R.

Satyanarayana,

J.

Inorg.

Nuclear

Cbm.,

1966,28,

2432.

099

(a)

$.

N.

Nabi

and

M.

S.

Amin,

J.

Ohem.

SOC.

(A),

1966, 1018;

(b)

L.

Almaai

and

99, 3108.

A.

Hantz,

Chsm.

Ber.,

1966,

99,

3288;

(c)

K.

Emerson,

Ada

Cq8t.,

1966,

21,

970.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

DOWNS,

EBSWORTH

AND

TURNER:

THE

TYPICAL

ELEMENTS

181

pressures, SOC1, and Ag2S react together to give

S,O

(97%

purity); the

compound is monomeric as vapour, and (apparently)

in

dilute sohd solution

in

SO2

(yellow at

-196"),

but when condensed alone

it

forms red polymeric

material at this temperature, and the condensate gives an e.s.r. spectrum at

-150".

Neither SOC1,

nor

S,O

forms compounds with BF, at

-150",

but

both give

1

:

1

adducts with Me,N that may be sublimed

in

vmuo

and are

stable at room temperature.mb

Work

has continued

on

the adducts

of

SO2

with transition metals.401 Sulpholan forms a

1

:

1

adduct with

BF,

but

not

with

PF,

(though

in

the latter case there

is

evidence

of

reaction).a2

The action

of

NO2 on HS0,Cl gives HS,O,NO; this or related com-

pounds

403=~

b

are formed in the reactions between N02C1 and HSO,Cl, and

between N02C1 and

SO,.

The dissociation constant of methanesulphonic

acid from Raman spectra is

m.

73

molefitre,

so

the acid

is

stronger than

nitric acid.404 The thermal decompositions

of

sulphamic acid

4055

and

of

sulphamide

405b

are complex processes; from the latter, a number of new

S-N

oxyacid derivatives

has

been isolated. The action of

KF

in

CH&N

on

(NSOCl), gives

406

(NSOF),, of which the pure cis-isomer has been isolated;

it

reacts with PhLi to give Ph,PO,S,N,, and with benzene

in

the presence of

AlCl,

to give two forms of (NSOPh),. Chlorination

of

AgN(SO,F), gives

407

ClN(SO,F),, which photolyses to form (FSO,),N,, adds to

CO,

ClCN, and

BrCN, and gives

a

salt

of

NO+

with

NO.

Cryoscopy in HS0,F has been

described,408a and the equilibria betyeen

H20

(giving

HF

and

H2S04)

or

KNO,

(giving

K+,

NO,+, and

H,O+)

and the solvent have been investigated

by

cryoscopy and conductometry.408b Values

for

lSF

chemical shifts in

OS0,F-deriva tives have been collected

.

*Og

Recent progress in sulphur-fluorine chemistry has been re~iewed.~lO~

Aluminium chloride reacts

41°b

with R,N: SF, to give

R,N:

SCl,, which with

Ag20 forms RFN:S:

0.

Treatment of Si(NCO), with

SF40

in

the presence

of

BF, gives OSF,NCOF, which forms an adduct with

Csl?;

the action

of

X,

(X

=

F

or

Cl)

on this adduct gives O:SF,:NX, decomposed by ultraviolet

irradiation. The preparation of

SNClF,

(probably SF,:NCl) from NSF and

C1,

in the presence of CsF,

or

from SF,NCOF, CsF, and C1,

in

a static system,

is described; an unstable material, perhaps SF,NBr,

was

obtained from

NSF,

CsF,

and

Br,,

but attempts to make SF2NF were unsucce~sful.~~~

The new compound SF5NH, has been prepared from NSF, and

KE

at room

400

P.

W.

Schenk

and

R.

Steudel,

2.

anorg. Ch.,

1966,

342,

(a)

p.

253;

(b)

p.

263.

401

F.

A.

Hartman and

A.

Woicicki,

J.

Amer. Chem.

Soc.,

1966,

88,

844;

L.

Vasks

(02

J.

G.

Jones, Inorg. Chem.,

1966,

5,

1229.

40s

(a)

M.

Wartel,

S.

Noel,

and

J.

Heubel,

Compt.

rend., Ser.

C,

1966,

862,

921;

404

J.

H.

R.

Clarke

and

L.

A.

Woodward, Trans.

Paraday

SOC.,

1966,

62,

2226.

406

(a)

W. Wanek,

2.

Chem.,

1966,6,423;

(6)

K.

Nara,

M.

Nakagaki,

0.

Manabe,

and

'06

T.

Moeller

and

A.

Ouchi,

J.

Inorg. Nuclear Chem.,

1966, 28,2147.

407

J.

K.

Ruff,

Iwrg.

Cherra.,

1966,

5,

732.

408

(a)

R.

J.

Gillespie,

J.

B.

Milne,

and

R.

C.

Thompson, Inorg.

Chem.,

1966,5,468;

40B

F.

A.

Hohorst

and

J.

M.

Shreeve,

Inorg.

Ch.,

1966,

5,

2069.

410

(a)

S.

M.

Williamson,

Progr. Inorg.

Chm.,

1966,

7,

39;

(b)

M. Lustig,

Inorg.

and

S.

S.

Bath,

ibid.,

p.

1333.

(b)

K.

Stopperka and

V.

Grove,

2.

anorg.

Chem.,

1966,

347,

19.

H.

Hiyamct,

Hog0

Kagaku

Zassha',

1966,

69,

20.

(b)

R.

J.

Gillespie,

J. B.

Milne,

and

J.

B.

Senior,

ibid.,

p.

1233.

Chem.

,1966,

5,

1317;

(c)

J.

I(.

Ruff,

&id.,

p.

1787.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

182

INORGANIC

CHEMISTRY

temperature;411a fluorination of

S4N4

with

*In

F2/N2

at

O",

or

treatment

4110

of

NSF,

with

SF4

in

the presence

of

BF,,

gives

SF,N:SF,.

The adduct

(Me3N)&3F6Cl, formed at low temperatures, decomposes

to

SF4

and

(MeaN),CIF on warming to room temperature ;41Zu the compound MeNSFa

is

obtained from MeNH, and SF,C1

or

SF,, and the latter process also gives

(MeN),S. Irradiation

412b

of a mixture of SF,C1

or

SF,

with ClN(CF,), leads

to

the formation

of

(CF3),NSF,. The acceleration

of

the decomposition of

But202 by

sF6

has been put down

to

the attack of Me radicals on SF,, and the

formation

of

MeF has been detected!ls4 Contrary to previous reports, no

reaction was detected

413b

between

SF,

and HI.

Selenium.

The chemistry of Se, Te, and

Po

has been described

in

a book.414

The thermodynamics of the direct reaction between Se and

H,,

giving SeH,,

do not after

all

show any anomaliea.*l5

In

Me,Se the angle at Se has been

found by microwave spectroscopy

416

to

be

96'11'

&

10'.

The action of

ammonia on Ph,SeCl, in CH,C12 gives

a

white crystalline solid, formulated as

[Ph,Se:N:SePh,]+Cl-, in which the C1 ion can be exchanged for other

anion^;^^'^

N,Se, has the same cage-like structure as

N,S,,

but

the packing

in

the lattice

is

The chemistry of inorganic SeO-compounds has

been revie~ed.4~~~ Treatment of SeOC1, with NaOOCCH,

or

(COOAg),

gives

4lSb

the SeO-derivative of the organic acid; the oxalate is monomeric

in dioxan, and

is

described as containing 3-co-ordinated

Se.

The action of

MX

on SeOX,

(&I

=

alkali metal;,

X

=

IF,

C1, OMe, OEt) gives

,ls0

M+[SeOX,]

-

;

the alkoxides in alcohol are almost completely dissociated into

Se(OR), and

OR-

and are decomposed by CO,, giving SeO(OR),.

Several

cornplexea

of

metals with Ph,SeO have been prepared.418d Selenium trioxide

dissolves unchanged in POCl,

or

S02C1,,

and in solution is reduced

by

SOCI,

or PCl,, the products depending on the sol~ent.4~~a Crystalline com-

pounds

419b

SeO,,I,OS and I,0,,2Se03,H,0 have been obtained from SeO,

and

I,O,

or

HIO,;

polyselenate anions and protonated speciea have been

detected4204 by Raman spectroscopy in solutions

of

SeO,

in

anhydrous

H,Se04, and polyselenates have been prepared from SeO, and alkali metal

carbonates

or

~elenates.4~0b Acidity functions

of

selenic acid have been

determined, using indicators.42w The species formed

by

dissolving Sea, in

'11

(a)

A.

F.

ClifTord

and

I;.

F.

Duncan,

Inorg.

Ch.,

1966,

5,

692;

(b)

B. Cohen,

T.

R.

Hooper,

and

R.

D.

Peacock,

Chern.

Cornrn.,

1966,

32;

(c)

A.

F.

Clifford and

J.

W.

Thompson,

Inorg.

Chern.,

1966,

5,

1424.

41a

(a)

B.

Cohen and

A.

G.

MacDiarmid,

J.

Chern.

SOC.

(A),

1966, 1780;

(b)

R.

C.

Dobbie,

ibid.,

p.

1555.

nS

(a)

L.

Batt

and

F.

R.

Chickshank,

J.

Phys.

Chm.,

1966,

70,

723;

(b)

J.

R.

Case

and

H.

L.

Roberts,

1n:;g.

Chem.,

1966,

5,

333.

K.

W.

Bagnall,

416

J.

R.

Rawling and

J.

M.

Toguri,

Canad.

J.

Chern.,

1966,44,461.

410

J.

F.

Beecher,

J.

Mol.

Spectroscopy,

1966,

21,

414;

K.

H.

Linke

and

F.

Lemmer,

2.

awg.

Ch.,

1966,

345,

203.

(a)

R.

Appel

and

(3.

Buchler,

2.

anorg.

Chem.,

1966,848,176;

(b)H.Bhighausen,

T.

von

Volkmann,

and

J.

Jander,

Ada

Cqst.,

1966,21, 671.

418

(a)

R.

Paetzold,

Fortschr.

Chem.

It'orsch., 1966,

S,

690;

(b)

R. Pmtzold,

2.

Chem.,

1966,6,72;

(c)

R. Pmtzold and

K.

Aurich,

ibid.,

p.

152;

(d)

R.

Pmtzold and P. Vordank,

2.

anorg.

Chm., 1966, 347, 294.

'lS

(a)

E.

Class,

Experientia,

1966,

22,

133;

(b)

G.

Kempe

and

D.

Robus,

2.

Chem.,

1966,

5,

394.

410

(a)

R.

Paetzold and

H.

Amoulong,

2.

arz.org.

Chem.,

1966,

843,

70;

(b)

a.

Kempe

The Chemistry

of

Se,

Te

and Po,"

Elsevier,

1966.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

DOWNS, DBSWORTH

AND

TURNIR:

THE

TYPICAL

ELEMENTS

183

liquid Se have been described

in

chemical terms42l

8s

2Se-t. and 2C1-;

crystalline Me,SeI contains

422a

ion-pairs of

I-

and pyramidal Me,%+.

There is

no

evidence

in

the infrared spectra

of

salts

of

SeXe2- or TeX,,-

of

distortion of the

Tellurium.

In

crystalline [(MeO),P(S)S],Te, the co-ordination at Te can

be regarded as square-planar, with STeS angle

of

95.7"

and weak Te-S inter-

actions with two other

S

atoms:423a the crystal

of

Te(tu),(HF,),

(tu

=

thiourea) contains a binuclear cation, with Te

in

a distorted square-

planar and

in

PhTe(tu),Cl the

Te

atom

in

the PhTe(tu)%+

ion

is

in

a square-planar environment with one position ernpty.4,3c

A

review

of the oxides and oxyacids of Te has The infrared spectra

of

TeX,

(X

=

C1,

Br,

I)

are consistent with the formulation

of

the compounds as

TeX,+X-, and no evidence was obtained for the presence of molecules in the

s0lid;~~5" the compounds MTeF5

(M

=

alkali metal,

NH4+,

pyH+) are

formulated

on

the basis of their vibrational spectra and the conductivity and

molecular weight

of

the pyridinium derivative

in

methanol

or

pyridine

as

salts, with Te in

a

square pyramid

of

F

atoms.425b The anions TeC1,2-

[in (NH,),TeCI,J

426a

and

TeBr,2-

[in

(NH4)2,

Cs,TeBr,] are undistorted,426b

at least

to

a

considerable degree

of

precision.

Group

VII.-Solid-state galvanic cells have been

used

427

to determine

AG,"

for

several fluorides. The chemistry

of

bromine has been described in

a

book

42ga

and

a

re vie^.^,^^

The oxidation

of

I,

by

different amounts

of

S206F2 in fluorosulphuric acid has been investigated spectroscopically, and

using measurements of conductivity, molecular weight, and magnetic suscep-

tibilit~:"~ with excess of

S20,F2,

I(So,E"),

is f~rmed;~*~a with

I,

:

S206P2

of

1

:

1

and 2

:

I,

the species

I,+

is prod~ced.4~~* The

U.V.

spectrum

of

I,+

is

identical

429c

with that

of

the species obtained on dissolving

1,

or

IC1

in

65%

oleum

or

I,

in

IF5

and previously attributed

to

I+.

The

fist

complex salts

have been prepared

430

containing halogen/nitrate anions [Me,NI(NO,),,

Me,NI(NO,),; Me,NBr(NO,),]; the preparation

of

I(SCN),-

by

oxidation

of

12/SCN- solutions has been c0nfirmed,~31~ and infrared spectroscopy

shows

that

in

M(I>~),(NCS),(I~)~

[M

=

CO(II),

Ni(rr)] one iodine molecule is bound

and

D.

Schmitt,

2.

Chem.,

1965,5,427;

(c)

D.

H.

McDaniel

and

L.

H.

Steinert,

J.

Amer.

4a1

M.

Lundkvist and

L.

G.

Sillh,

Acta

Chem. Scund.,

1966,

20,

1723.

428

(a)

H.

Hope,

Actu

Cryst.,

1966,20,610;

(b)

N.

N.

Greenwood and

B.

P.

Straughm,

J.

Chem.

SOC.

(A),

1966, 962.

Pas

(u)

H.

Husebye,

Acta

Chem.

Scand.,

1966, 20,24;

(b)

0.

Foss

and

S.

Hauge,

ibid.,

1965,19,2395;

(c)

0.

Foss

and

K.

Maroy,

ibid.,

1966,

20,

123.

424

W.

A.

Dutton and

W.

C.

Cooper,

Chem.

Rev.,

1966,

66,

657.

4a6

(a)

N.

N.

Greenwood,

€3.

P.

Straughan, and

A.

E.

Wilson,

J.

Chem.

SOC.

(A),

1966, 1479;

(a)

N.

N.

Greenwood,

A.

C.

Sama,

and

B.

P.

Straughm,

J.

Chem.

SOC.

(A),

1966, 1446.

426

(a)

A.

C.

Hazell, Ada

Cbm.

Scud.,

1966,20,165;

(b)

A.

K.

Das and

I.

D.

Brown,

Cunad.

J.

Chem.,

1966, 44,939.

4*7

R.

J.

Heus and

J.

J.

Egan,

2.

phys.

Chem.

(Frankfurt),

1966,

49,

38.

(a)

"

Bromine and

its

Compounds," ed.

Z.

E.

Jolles,

Ernest

Benn

Ltd., London,

1966;

(b)

V.

A.

Stenger,

Angew.

Chem.,

Internact.

Edn.,

1966,

5,

280.

42s

R.

J.

Gillespie

and

J.

B.

Milne,

(a)

Inorg.

Chem.,

1966,

5,

1236;

(b)

Chern.

Comm.,

1966, 158;

(c)

Inorg. Chem.,

1966,

5,

1577.

430

M.

Lustig and

J.

K.

Ruff,

Inorg.

Chem.,

1966,

5,

2124.

ch.

soc.,

1966,88,4826.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

184

INORGANIC

CHEMISTRY

to

one

thiocyanate Many other iodine complexes have, been

studied;

infrared

spectra suggest

432a

that in the following complexes the

order of strength

is

pyI,

<

pyIBr

<

pyIC1;

in

dioxan, I,/trialkylamine

complexes are probably ion-pairs ;432b the complexes between

I,

and amino-

boranes are probably bound by 1,-N o-bonds rather than by n-interactions

from

the

B-N

bonds;135a

U.V.

spectra give evidence for the persistence

of

1

:

1

complexes between

I,

and

Et20

or

benzene in the vapour phase,432~

md

py,ZI,

has been detected

in

the gas phase by mass spectrometry.-432d The

role

of

solvent

has

been empha~ised,Q~~~ and gas-solid chromatography em-

ployed.a2'

Ion-pairs and complexes

of

I-

have

been

investigated by

u.~.

spectros~opy:~~ and evidence has been obtained for the formation of the

complex

I

***

I-H

on photolysing

EtI

in

a hydrocarbon matrix434 at

77°K.

Organic polyvalent iodine compounds have been reviewed.435

Mass

spectra have given evidence

436

for

the formation of HAt, MeAt, AtI, AtBr,

and

AtCl, but there was no indication of At,.

The

lH-

and l9F-n.m.r. spectra

of

solid KH,F3 indicate that the H-bond

potential function

is

not symmetrical

437 (cf.

HI?,-).

The preparations of

43g0

R,N+(FHX)-(X

=

Cl,

Br,

I)

from

R,NX

and gaseous

HF

and

of

43gb

Me,N+

(CIHN0,)-

are confirmed by infrared spectroscopy. The potential function

in R4N+HCl,-

(It

=

Et, Pr*, n-Pent) is apparently symmetric; infrared

spectra

4390

are said

to

indicate that

in

M+HC12-

(M

=

Cs,

Me4N,

Bun4N)

the potential function has a single asymmetric minimum, but

a

single

chlorine

NQR

signal was observed.439b

The compound obtained from

gaseous HC1 and saturated aqueous

CsCl

is

shown

by X-ray diffraction to

be CsC1,1/3(H30+.HCl,-) and hence the

first

measurement of

the

Cl-Cl

distance

in

a bichloride

is

obtained.*39c

A

photolytic preparation of ClF,

at

room

temperature and one atmosphere pressure has been des~ribed.~40

The pentagonal bipyramid structure of

IF,

has been codirmed?41

Vibrational spectra suggest that the ClF4- ion

is

square-planar in the

Rb

and

Cs

salts, but not

442a

in NO+C1F4-; that C1,-

is

linear and symmetric in

the Et4N+,

Prn4N+,

and Bun4N+ ~alts;~42~ that the

C1,-

ion

is

present in

a1

(a)

C.

Long and

D.

A.

Skoog,

Inorg.

Chem.,

1966,5,206;

(b)

D.

Forster

and

D.

M.

L.

Goodgame,

J.

Chem. SOC.

(A),

19G6, 170.

r3z

(a)

S.

G.

W.

Ginn

and

J.

L.

Wood,

Tram. Paraday SOC.,

1966,

62,

777;

(b)

K.

Toyada

and

W.

B.

Person,

J.

Amer.

Chem. SOC.,

1966,

88,

1629;

(c)

F.

T. Lang and

R. L.

Strong,

ibid.,

1965,

87,

2345;

(d)

R.

Cahay and

J.

E.

Collins,

Nature,

1966,

211,

1175;

(e)

R.

S.

Drago,

T.

F.

BoIles, and

R.

J.

Niedzielski,

J.

Amer.

Chem.

SOC,,

1966,

88,

2717;

(f)

R.

J.

Cvetanovi6,

F.

J.

Duncan,

W.

E.

Falconer, and

W.

A. Sunder,

ibid.,

p.

1602.

433

M.

J.

Blandamer,

T.

E.

&ugh, and

M.

C.

R.

Symons,

Trans. Paraday SOC.,

1966,

62,

28G,

301.

434

D.

Timm,

Acta

Chem.

Scand.,

1966,

20,

2219.

435

D.

F.

Banks,

Chem.

Rev.,

1966,

66,

243.

IS6

E.

H.

Appelman

E.

N.

Sloth, and

M.

H.

Studier,

Inorg.

Chem., 1966,

5,

766.

43'

R.

Blinc,

Z.

Trontelj, and

B.

Volavgek,

J.

Chem.

Phys., 1966,

44,

1028.

(a)

6.

C.

Evans

and

G.

Y.-S.

Lo,

J.

Phys.

Chm.,

1966,70,543;

(b)

J,

A.

Salthouse

and

T.

C.

Waddington,

J.

Chem.

SOC.

(A),

1966, 28.

43O

(a)

J.

C.

Evans and

G.

Y.-S.

Lo,

J.

Phys.

Chem.,

1966,70, 11;

(b)

J.

C.

Evans

and

G.

Y.-8.

Lo,

ibid.,

p.

2702;

(c)

L.

W.

Schroeder and

J.

A.

Ibers,

J.

Aw.

Ch.

SOC.,

1966,88, 2601.

440

R.

Gatti,

R.

I;.

Krieger,

J.

E.

Sicre,

and

H.

J.

Schumacher,

J.

Inorg.

Nuclear

Chem.,

1966,

28,

655.

441

H.

B.

Thompson,

end

L.

S.

Bartell,

Trans, Amer. Crgst.

ASSOC.,

1966,

2,

190.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

DOWNS,

EBSWORTH

AND

TURNER:

THE

TYPICAL

ELEMENTS

185

acetonitrile solution when

442b

C1,

:

C1-

>

1;

that the ClBr,- ion has the

linear arrangement

442c

ClBrBr-; and that the ions I,Cl,-, 12C12Br-, and

12ClBr2- are present

442d

in the

1

:

1

adducts

of

BHIC1,

(B

=

pyridine-type

base) with IC1 and IBr and

of

BHIBr,

with IC1. X-ray diffraction shows

that Cs1,Br is isostructural with CsI,, and that the

BrII-

ion is n~n-linear.~~~

The stability constants

of

Br2C1- and BrC1,- in aqueous solution have been

determined from redox potentials

;Ireaa

the stability constants of Br3- and

Br,-

are sensitive to changes in ionic strength;444b the reaction

in

liquid HC1

of halogens and interhalogens with halide lion has been studied conducto-

rnetri~ally.4~~ In KICl, and KICl,, Mossbauer

(

12'1)

spectroscopy

favours

446

a model with delocalized orbital bonding and with little

or

no

contribution from the s-orbitals of the

I

atoms. The adduct BrF3,BF3

is

said

to be stable only

447a

up

to

-80"

and

to

melt with decomposition

447b

at

180";

infrared spectra suggest that this adduct may be represented

447b

by

BrF,+ BF4-, but that 2BrF3,GeF4 does not consist of BrF,+ and GeFe2-

ions.447a

Iodine

trifluoride forms

1

:

1

adducts

448

with BF,,

AsF5,

and SbF,

which may contain the species

IF,+.

442

(a)

K.

0.

Christie

and J. P. Guertin,

Inorg.

Chem.,

1966,

5,

473;

(b)

J.

C.

Evans

and

G.

Y.-5.

Lo,

J.

Chem.

Phys.,

1966,

44,

3638;

(c)

J.

C.

Evans and

G.

Y.-S.

Lo,

ibid.,

1966,

46,

1069;

(d)

Y. Yagi and

A.

I.

Popov,

Inorg.

Nuclear Chem. Letters,

1965,

1,

21.

443

G.

B.

Carpenter,

Acta

Cryst.,

1966,

20,

330.

444

(a)

R.

P. Bell and

M.

Pring,

J.

Chem.

SOC.

(A),

1966,1607;

(6)

V.

E.

Mironov and

N.

P.

Lastovkina,

Rws.

3.

Inorg.

Chem.,

1965,10,687;

V.

E.

Mironov

and

N.

P.

Lastov-

kina,

{bid.,

1966,

11,

314.

445

J.

A.

Salthouse and

T.

C.

Waddington,

J.

Chem.

SOC.

(A),

1966, 1188.

446

G.

J.

Perlow

and

M.

R.

Perlow,

J.

Chem.

Phys.,

1966,

(C),

45,

2193.

447

(a)

D.

H.

Brown,

K. R.

Dixon, and

D.

W.

A.

Sharp,

Chem.

Comm.,

1966, 654;

448

M.

Schmeisser and

W.

Ludovici,

2.

Naturforsch.,

1965,

20b,

602.

(b)

M.

S.

Toy

and

W.

A.

Cannon,

J.

Phys.

Chem.,

1966,

70,

2241.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

4.

THE TRANSITION

ELEMENTS

By

F.

E.

Mabbs

and

I).

3.

Machin

(Chembtry

Department,

Ths

Uniuersity, Mancheater,

13)

As

in

previous years, transition-metal chemistry

will

be reviewed by dividing

the elements into groups. Compounds

will

be discussed generally

in

order

of

increasing oxidation state of the metal. Papers dealing with elements

from

a

number

of

groups

will

usually

be

mentioned

only

once.

It

has been

necessary, once again,

to

omit any reference

to

the large amount

of

work

being published in the field of solvent extraction

of

metals.

It

is

impossible

to

cover

this

field adequately

in

the space available.

General reviews which have appeared during the year include

a

dis-

cussion

of

five-co-ordination, and the chemistry of compounds containing

metal-atom c1usters.l Schiff base and /I-keto-amine complexes, nitric oxide

compounds of the transition-elements, and 18-keto-enolate complexes have

been considered,2 as well as the Cotton effect in co-ordination compounds.s

Scandium

and

the

Lanthanides.-Two equilibrium compounds, 3NaFScFs

(cryolite-type) and NaPScF, (hexagonal), have been found

4

in

the sodium

fluoride-scandium fluoride system. The ternary oxide MgSc,O, has been

prepared

at temperatures above

2000"~.

Its

structure

is

similar to that

of CaSc,O, and CaFe,O,. Hydrolysis studies

of

scandium(m) perchIorate

by means

of

ultracentrifugation have established

The nature

of

solutions of europium and ytterbium

in

liquid ammonia,,

discussed last year, has been confirmed by studies of their electronic spectra.'

Phase studies

8

of

the lanthanide sesquioxides at very high pressures and

temperatures have been described, and the tungsten bronzes

lb&.lWO,

p:e-

pared

9

for thirteen lanthanides; their magnetic properties were also

dis-

cussed.

Lanthanide titanates MTiO, can be prepared for

a

number of

lanthanides, M. The formation

of

oxide-carbides NdC,O, and

MC,O

(M

=

Y,

Sc)

has been observed.ll The published structure

of

lanthanum(m) fluoride

has been shown to be incorrect. The corrected structure

12

has nine nearest-

neighbour fluoride ions. The lanthanide elements and their nitrides

13

have

interesting magnetic properties.

the species present.

E.

L.

Meutterties and

R.

A.

Schum,

Quart.

Rev.,

1966, 20,

246;

F.

A.

Cotton

a

R.

H.

Holm,

G.

W.

Everett, and

A.

Chakravorty,

Prog. Iwg.

Chem.,

1966,

7,

3

R.

D.

Gillard,

Prog. Inorg.

Chem.,

166,

7,

216.

4

R.

E.

Thoma

and

R.

H.

Karraker,

Inorg.

Chem.,

1966,5, 1933.

6

J.

Aveston,

J.

Chem.

Soc.

(A),

1966, 1699.

*

H.

R.

Hoekstra,

Inorg.

Chem.,

1966,

5,

764.

0

W.

Ostertag,

Inorg.

Chem.,

1966,

6,

768.

aid.,

p.

389.

83;

B.

F.

G.

Johnson and

J.

A.

McCleverty,

ibid.,

p.

277;

J.

P.

Fackler,

ibid.,

p.

361.

H.

Miiller-Buschbaum,

2.

anorg.

Chem.,

1966,

343,

113.

D.

S.

Thompson,

D.

W.

Schaefer,

and

J.

S.

Waugh,

Inorg.

Chem.,

1966,

5,

326.

10

H.

Holzapfel and

J.

Sieler,

2.

unorg.

Chm.,

1966,

343,

174.

11A.

D.

Butherus,

R.

B.

Leonard,

G.

L.

Buchel,

and

H.

A.

Eick,

Inorg.

OM.,

1966,

5,

1667.

la

A.

Zalkin,

D.

H.

Templeton, and T.

E.

Hopkins,

Inorg.

Chem.,

1966,

5,

1466.

18

D.

P.

Schumecher and

W.

E.

Wallance,

Inorg.

Chem.,

1966, 6, 1663.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

MABBS

AND

MACHIN:

THE

TRANSITION

ELEMENTS

187

New preparations for praesodymium and neodymiun(m) azides,l*

a

number of alkoxides,l5 and cyclopentadienyl complexes

l6

have been des-

cribed. The mass spectrum of caesium

tetrakis-hexafluoroacetylacetonato-

yttrium(m) shows

l7

that the ion Cs~(acacF,),]+ is particularly, and

un-

expectedly, stable. Some

1

,lo-phenanthroline, dibenzoylmethane, and

2,2'-bipyridyl complexes have been reported, and their fluorescent pro-

perties discussed.ls Tris-chelates of y-isopropyltropolone with lanthanide

ions are associated, leading to seven-co-ordinated structures. Monothio-

tropone complexes are similar to those of tropolone,

e.g.,

tetrakisthiotropone-

thorium(

IV)

is

formed

;

however,

bisisopropyltropolonenickel(n)

is associated

and paramagnetic in solution, whilst the thiotropone analogue is diamag-

netic.lg Anomalies in the intensities

of

neodymium and erbium triethylene-

tetraminehexa-acetate complexes have been explained.20

The

Actinides.-The chemistry

of

protactinium has been reviewed.21

Radiochemically pure 239Np has been isolated

22

by reversed-phase chroma-

tography. Neptunium(@ oxide is the only product formed

23

on heating

NpO,

in

vaeuo.

Attempts to oxidise americium(m) with perxenate in basic

solution led instead

24

to

the isolation

of

the complex species

Am,(Xe0,)3,40H,0.

If

the solution is acidified, americium-(v) and

-(vI)

are formed.

The quadrivalent fluorides,

LiMF,

(M

=

Np,

Pu, Am, Cm), have been

prepared

25

by reduction

of

the quinquevalent species. The complex halides,

Et,NMX

(M

=

Th

or

Pa,

X

=

C1

or

Br), have been characterised

26 to-

gether with protactinium(Iv) chloride and bromide. Detailed studies of the

electronic spectra and magnetism of uranium(rv) hexahalide complexes,

and phosphine oxide complexes

of

UC1, and

UBr,

have appeared.27

Thor-

ium(rv) forms eight-co-ordinated urea complexes,28 whilst tropolone and

y-isopropyltropolone form ten-co-ordinated species.29

l4

V.

Gutmann,

0.

Leitmann, and

R.

Schutz,

Inorg. Nuclear Chem. Letters,

1966,

2,

133.

l5

K.

S.

Mazdiyasni,

C.

T.

Lynch, and

J.

S.

Smith,

Inorg. Chem.,

1966,

5,

342.

l*

A.

F.

Ried and

P.

C.

Wailes,

Inorg. Chem.,

1966,

5,

1213;

F.

Calderazzo,

R.

Pappalardo, and

S.

Losi,

J.

Inorg. Nuclear Chem.,

1966, 28, 987.

l7

S.

J.

Lippard,

J.

Amer. Chem.

SOC.,

1966,

88,

4300.

la

N.

I.

Lobanov and

V. A.

Smirnova,

Rws.

J.

Inorg. Chem.,

1965,

10,

868;

E.

V.

Melent'eva, L.

I.

Kononenko, and

N.

S.

Poluetov,

ibid.,

1966,

11,

200;

S.

Herzog

and

K.

Gustav,

2.

anorg. Chem.,

1966,

346,

150;

S.

P.

Sinha,

J.

Inorg. Nuclear Chem.,

1966,

28,

189.

l9

E.

L. Meutterties,

H.

Roesky, and

C.

M.

Wright,

J.

Amer. Chem.

SOC.,

1966,

88,

4856.

2o

E.

A. Bourdreaux and

A.

K. Mukherji,

Inorg. Chem.,

1966,

5,

1280.

21

C. Keller,

Angew. Chem., Internat. Edn.,

1966,

5,

23.

22

S.

Lis,

E.

J.

Jozefowicz, and

S.

Siekierski,

J.

Inorg. Nuclear Chem..

1966, 28,

23

R.

J.

Ackerman,

R.

L. Faircloth,

E.

G.

Rauh, and

R.

J.

Thorn,

J.

Inorg. NucEear

24

Y.

Marcus and

D.

Cohen,

Inorg. Chem.,

1966,5, 1740.

25

T.

J.

Keenan,

Inorg. Nuclear

Chem.

Letters,

1966, 2, 153.

26

D.

Brown,

J.

Chem.

SOC.

(A),

1966, 766;

D.

Brown and

P.

J.

Jones,

Chern.

Comm.,

27

J.

P.

Day and

L.

M. Venanzi,

J.

Chem.

SOC.

(A),

1966, 197.

28

P.

S.

Gentile,

L.

S.

Campisi, and

P.

Carfagno,

J.

Inorg. Nuclear

Ch.,

1966,

199.

Chem.,

1966,

28,

111.

1966, 279.

28,

1143.

E.

L.

Meutterties,

J.

Am.

Chem.

SOC.,

1966, 88, 305.

G

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

188

INORGANIC

CHEMISTRY

The first neptunium(v) compounds to be prepared which

do

not contain

the Np02+ ion are

30

MINpFs

(MI

=

Na,

K,

Rb, Cs,

NH,)

and RbPpF,.

Subsequently, M1,Np0C1,

(MI

=

Cs,

Ph,As), Cs,Np0,C13, and CsapO,Cl,

were reported.31 Species MI,PaF,

(MI

=

K,

Rb,

Cs,

NH,)

and

MI,PaF,

(MI

=

Li,

Na,

K,

Cs)

have been de~cribed.~2

A

series

of

Papers

33

dealing

with protactinium(v) describe the preparation of the pentachloride and

pentabromide; PaOCJ, and PaOBr, are also formed, but in addition

some

Pa20Cl, is produced. The latter decomposes

in

vacuo

to Pa,03C1,, then

to

Pa02C1. Protactinium(v) chloride forms mono-adducts with the phosphine

oxides R3P0

(R

=

Ph

or me,). The nitrate complexes M1Pa(N03),

(MI

=

Cs,

NhIe,,

or

NEt,) were prepared from

the

corresponding chlorides;

more complex species result if the chlorides react with various oxides

of

nitrogen.

The uranyl triperoxide ion in Na4U02(0,),,9H,0 has been shown

34

to

have a structure in which the three peroxide groups lie in a plane, with all

six

oxygens co-ordinated to the uranium. Compounds

MIUP,

and

Mr,UF',

(MI

=

Na

or

K)

have been ~haracterised.~5

It

is claimed

36

that uraniurn-

(IV)

and

-

(VI)

triphenylphosphine complexes previously reported cannot be

prepared, and that the species isolated are, in fact, uranyl-phosphine oxides,

UO2C1,(Ph3PO),. Reduction of UO,Cl, in cyclohexanol

in

the presence

of

triphenylphosphine yields

a

clathrate, UC1,(Ph3P),,C6Hl1OH.

Titanium,

Zirconium,

and

Habium.-A

method for the separation of

zirconium and hafnium, based on the distribution

of

their thiocyanates

between water and methyl isobutyl ketone, has been proposed.37

A

solution

of

zirconium tetrabromide in tetrahydrofuran precipitates ZrBr,(diars),

immediately

on

addition

of

o-phenylenebisdimethylarsine

(diars)

,38

whilst

the hafnium compound forms only slowly, offering an alternative separation.

The compounds formed are isostructural with TiCl,( diars),. Under aimilar

conditions, TiF, forms (TiF,),diars, and TiI, yields TiI,(diars),, which

is

not

isomorphous with the chloride.

The preparation of two cyclo-octatetraene (cot) complexes, Ti( cot)

and Ti,(cot),

from

Ti(OC,N,), has been reported. The structure

of

the

dimer shows that

one

cot

ring

lies between the titaniums, with Ti-C

"

bond

"

lengths ranging from

2-29

to

2.57

A;

only the non-bridging rings

30

L.

B.

Asprey,

T.

K.

Keenan,

R.

A. Penneman, and

G.

D.

Sturgeon,

Inorg.

Nudear Chem. Letters,

1966,

2,

19;

L.

B.

Asprey,

F.

H.

Kruse,

A.

Rosenweig, and

R.

A.

Penneman,

Inorg.

Chem.,

1966,

5,

659.

31

K.

W.

Bagnall and

J.

B. Laidler,

J.

Chern.

Soc.

(A),

1966, 516.

32

D.

Brown and

J.

F.

Easey,

J.

Chem.

SOC.

(A),

1966, 254;

M.

N.

Bucklish,

J.

Flegenheimer,

F.

M.

Hall,

A.

G.

Meddock,

and

C.

Ferreira de Miranda,

J.

Inorg. Nuclear

Chem.,

1966,

28,

421.

33

D. Brown,

J.

F. Easey,

and

J.

G.

H.

du

Preez,

J.

Chem.

Xoc.

(A),

1966, 258;

D.

Brown

a,nd

P.

J.

Jones,

ibid.,

pp.

262,

733,

and

874.

34

N.

W.

Alcock,

Chem.

Comrn.,

1966,

536.

35

J.

G.

Malm,

H.

Selig, and

S.

Siegel,

Inorg. Chem.,

1966,

5,

130.

ssB.

W.

Fitzsimmons,

P.

Gans,

B.

Hayton, and B.

C.

Smith,

J.

Inorg. Nuclear

37

W.

Fischer,

B.

Deierling,

H.

Heitsch,

G.

Otto,

H.-P.

Pohlmann,

andK. Reinhardt,

38

R.

J.

H.

Clark,

W.

Errington,

J.

Lewis,

and

R. S.

Nyholm,

J.

Chem.

SOC.

(A),

Chem.,

1966,

28,

915.

Angew.

Chem.,

Internat.

Edn.,

1966,

5,

15.

1966,

989.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

MABBS

-4ND

MACEXN:

TEE TRANSITION ELEMENTS

189

are planar.39

Titanium and zirconium diborides have been synthesised,**

as well

as

two hafnium sulphides,41

WS

and

Hf,S.

The electronic spectra of a-TiC1, and Cs,Ti,Cl, have been re-interpreted,dz

the higher energy band being attributed to a chasge-transfer process.

Calculations have been performed to obtain energy-level diagrams for ions

[MF,Is-

(M

=

Ti,

V,

Cr, Fe,

Cop3

Thermodynamic and electrochemical

studies of zirconium-(m) and

-(n)

chlorides in molten Na-KC1 have been

described.44 The first hexachlorotitanate(rn) complex, (pyH),TiCl,, has

been described,45 as well as Et4NTiCl4,2MeCN and Et4NTiC1,Br,2MeCN.

The adduct (Me,N),TiBr,

has

been shown

46

to have a trigonal-bipyramidal

structure, and the structure of p-ZrC1, has also been elucidated.47

When

dicyclopentadienyltitanium

dichloride reacts with dialkyl or diary1 sulphides,

the product is either cp,TiCl(SR)

48

or

C~~T~(SR),.~~ The former authors

only obtained the disubstituted species by reaction of cp2TiC1, and the

sodium salt of the corresponding thiol (cp

=

cyclopentadiene). The inter-

mediate, (cp,TiH),, in the Vol'pin and Shur nitrogen fixation process has

been studied.50

The hexafluorohafnate(rv) ion has been prepared

51

as the hydrazinium

salt; (N2H6),Hf2FI4 has also been obtained. The alkali metal salts M1,ZrC1,

are precipitated

52

from a solution of ZrOC1, and MIC1. The far-infrared

spectra of titanium and vanadium tetrachlorides have been assigned,53 and

used to calculate thermodynamic data

for

gaseous VCl,. The heats of

reaction

of

a number of titanium, vanadium, and chromium tetra-alkoxides

have been reported.

54

Complexes of

hexamethylcyclotriphosphazene

with

titanium and tin tetrachlorides have been prepared, their formulation

being

s5

(Me,PN),MCl,. Although

o-phenylenebisdimethylarsine

forms eight-

co-ordinate adducts with titanium(

IT),

the corresponding diethylarsine or

phosphine only form six-co-ordinate complexes, whilst the dimethylphosphine

yields eight-co-ordinate species.

It

is concluded

56

that steric factors are

responsible for the differences.

A

number of bidentate sulphur ligands

only

form

1

:

1

adducts with the chlorides

MC1,

(3%

=

Ti, V, Sn),57 whilst the

triarsines bis-

(o-dimethylarsinopheny1)methylarsine

and tris-1

,l

,1-(dimethyl-

3s

H.

Breil and

G.

Wilka,

Angew. Chern., Internat. Edn.,

1966,

5,

898.

40

L.

Barton and D. Nicholls,

J.

Inorg.

Nuclear Chem.,

1966,

28,

1367.

41

H.

F.

Franzen and

J.

Graham,

J.

Inorg. Nuclear Chem.,

1966,

28,

377.

42

C.

Dijkgraaf,

J.

P.

C.

van Heel, and

J.

P.

G.

Rousseau,

Nature,

1966,

211,

185.

43

R.

F.

Fenske, K.

G.

Caulton,

D. D.

Radtke, and

C.

C.

Sweeney,

Inorg. Chem.,

44

B.

Swaroop and

S.

N.

Flengas,

Canad.

J.

Chem.,

1966,

44,

199.

46

B.

T.

Russ and

G.

W.

A.

Fowles,

Chem. Comm.,

1566, 19.

46

B.

J.

Russ

and

J.

S.

Wood,

Chem. Comm.,

1966, 745.

47

J.

A.

Watts,

Inorg. Chem.,

1966,

5,

281.

48

R.

S.

P.

Coutts,

J.

R.

Surtees,

J.

M.

Swan, and

P.

C.

Wailes,

AusfraE.

J.

Chem.,

49

H.

Kopf and

M.

Schmidt,

2.

anorg. Chem.,

1965,

340,

139.

50

H.

Brintzinger,

J.

Amer. Chem.

SOC.,

1966,

88,

4305, 4307.

51

J.

Slivnik, B. Jerkovic, and B. Sedej,

Monatsh.,

1966,

9'7,

820.

52

G.

M.

Toptygina and

I.

B.

Barskaya,

Russ.

J.

Inorg.

Chem.,

1965,

10,

1226.

63

J.

A.

Creighton,

J.

H.

S.

Green, and

W.

Kynaston,

J.

Chem.

SOC.

(A),

1966, 208.

54

D.

C.

Bradley and

M.

J.

Hillyer,

Trans.

Paraday

SOC.,

1966,

62,

2367.

65

M.

F.

Lappert and

G.

Srivastava,

J.

Chem.

SOC.

(A),

1966, 210.

66

R.

J.

H.

Clark,

R.

H.

U.

Negrotti, and

R.

S.

Nyholm,

Chem. Comm.,

1966,

486.

57

R.

J.

H.

Clark and

W.

Errington,

Inorg. Chem.,

1986,

5, 650.

1966,

5,

960.

1966,19, 1377.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

190

INORGANIC

CHEMISTRY

arsinomethy1)ethane form

58

seven-co-ordinate adducts with TiC1, and VC1,.

A

number of mixed

n-cyclopentadienyl-maleonitrile-dithiolate

complexes

of

these elements have been rep0rted.~9

The structure

of

dichlorodiphenoxytitaniurn(rv)

is

a five-co-ordinate

dimer, involving phenoxy bridging groups.

6O

The structures of zirconium

and hafnium borohydrides have been deduced

61

from

llB

n.m.r. studies.

Details of the structure of Ti(NO,), have now appeared.62 The infrared

spectra of a large number of oxo-cations have been investigated;63 it

is

suggested that the range

of

frequencies expected

for

the metal-oxygen

vibrations is too narrow.

Vanadium,

Niobium,

and

Tantalum.-The metal-cluster compounds of

this group have received some attention this year.

A

@-form

of

Nb,Br8 has

been prepared

64

by heating the pentabromide and niobium metal; an iodide

can

be

made similarly. The triangular arrangement

of

the metal atoms is

retained, the Nb-Nb distance being

2.888.

It

is claimed that Nb6IIl

is

the fist M6x8 ion to be prepared

for

a

Group

V

element;

it

is formulated as

[Nb618]13, based

65

on X-ray evidence.

A

range

of

mixed metal compounds

[(Nb/Ta),Br,,]Br,,8H20 have been prepared,66 and it has been shown that

the ion ~b6C11,]

2+

is readily oxidised to [Nb6Cl1,]4+

;

the salt Nb6Cllp,3EfOH

being isolated. Similarly, [Ta6C1,J2+ may be oxidised by ferric ion to

[Ta6C1,,]4+

;

the intermediate tripositive ion is stable in this system, the

oxidation proceeding by two one-electron steps.

67

The far-infrared spectra

of

compounds M6X14 and

M6Xl4,8H2O

(M

=

Nb,

Ta;

X

=

C1,

Br)

have

been analysed.68 The crystal structure

69

of Ta6C114,7H,0 shows that the

six tantalum

atoms

form a tetragonally elongated octahedron.

It

is

claimed

7O

that species previously formulated

as

Ta,C1,,,7H20, HTa3C1,,4H,0,

or

Ta3C1,0,3H,0 are all Ta,Cl1,,8H20.

Vanadium(m) acetate and benzoate have been prepared from vanadium

diboride;

a

dimeric structure

is

proposed

71

with four bridging and

two

terminal carboxylate groups. Trigonal prismatic co-ordination of a

first-

row transition element has been established

72

in the tris-dithiolato-com-

pound V(S,C2Ph&. The very similar, (3.05-3.1

1

A),

sulphur-sulphur

distances in the rhenium, molybdenum, and vanadium compounds suggest

that

S-S

interactions determine the type of structure formed.

Complexes

68

R.

J.

H.

Clark,

M.

L.

Greedeld, and

R.

S.

Nyholm,

J.

Chem.

SOC.

(A),

1966,

59

J.

Locke and

J.

A.

McCleverty,

Inorg.

Chem.,

1966,

5,

1157.

6o

K.

Watenpaugh and

C.

N.

Caughlan,

Inorg.

Chem.,

1966,

5,

1782.

62

C.

D.

Garner and

S.

C. Wallwork,

J.

Chem.

SOC.

(A),

1966, 1496.

63

J.

Selbin,

Angew.

Chem.,

Internat.

Edn., 1966,

5,

712.

64

A.

Simon

and

H.

G.

von

Schnering,

J.

Less-Common Metds,

1966,11, 31.

65

L.

R. Bateman,

J.

F.

Blount, and

L.

F.

Dahl,

J.

Amer.

Chem.

SOC.,

1966,

88,

66

H.

Schiifer and B. Speckelmeyer,

J. Less-Common

Metals,

1966,

11,

73.

67

J.

H.

Esponson and R.

E.

McCarley,

J.

Amer.

Chem.

SOC.,

1966,

88,

1063.

88

P.

M.

Boorman and

B.

P.

Straughan,

J.

Chem.

SOC.

(A),

1966, 1514.

69

R.

D.

Burbank,

Inorg.

Chem.,

1966,

5,

1491.

70

H.

Schlifer and

D.

Bauer,

2.

anorg.

Chem.,

1965,340, 62.

71

N.

N.

Greenwood,

R.

V.

Parish, and P. Thornton,

J.

Chem.

SOC.

(A),

1966,

320.

72

R.

Eisenberg,

E.

I.

Stiefel, R,

C.

Rosenberg, and

H.

B. Gray,

J.

Amr.

Chem.

1254.

B.

D.

James, R.

K.

Nanda, and

M.

G.

H.

Wallbridge,

J.

Chem.

SOC.

(A),

1966,183.

1082.

SOC.,

1966,

88,

2874.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

MABBS

AND MACHIN:

THE

TRANSITION ELEMENTS

191

R+[VX4,2CH,CN]

(R+

=

Et,N, MePh,As, or Ph,As;

X

=

C1,Br) have been

prepared from VX3,3MeCN. The tetraethylammonium salt forms complexes

Et,N[VCl,,ZL] ligand

L

=

pyridine,

8

2,2'-bipyridyl, or

Q

1,lO-phenanthro-

line) by direct reaction, and desolvates at

100"c

to form

a

tetrahedral

species, Et,NVCl,.

Niobium tetrahalides slowly form

1

:

1

adducts with triethylamine, but

only

the chloride reacts completely

;74

the products are diamagnetic and

presumed to retain

a

dimeric structure. Several diamines also formed

1

:

1

complexes. The e.8.r. spectrum of vanadium tetra-t-butoxide shows

unexpectedly low g-~alues.7~ Several new vanadyl chloro-complexes have

been prepared and characterised

;76

they are formulated as M1,VOCl,,xH,O.

Five-co-ordinated structures are suggested

7'

for a number of vanadyl-Schiff

base complexes. Extended Huckel calculations

on

the vanadyl-porpkin

system have been published; energies for all of the

d-d

transitions are

calculated.78 Thermochemical data for pervanadyl

(VO,+)

and vanadyl

(VOZ+)

ions in solution are a~ailable.~~

in

a

study of the

Raman spectra of the system

Ta(v)-HF-NH,F-H,O

;

the octafluoro-ion

was not detected in solution.

Fluorotetrachlorotantalum(v)

is a tetramer

81

formed by bridging fluorine ions. A number of oxychloride compoundsy

e.g.,

VOC1, and POCl,, can be made

82

by reaction of aluminium chloride

with the oxide or an oxyion in molten Li-Na-KC1; TaOCl,

is

formed

s3

when TaCl, or M'TaCl, react with

Sb20,.

Assignments of the metal-oxygen

and metal-halogen frequencies have been made

84

for the infrared spectra

of

compounds M1,[MvOX5]

(MI

=

Rb,

Cs;

Mv

=

Nb, Mo, or

W;

X

=

C1,

Br).

Infrared and Raman studies

s5

of vanadate(v) solutions at various pH values

have also been described, and assignments proposed for the ions V0,3-,

HV04,-,

v2074-y

HV,0,3-, and (V03)1,n-. The molecular structure

of

the

isopolyvanadate ion

(V10028)6-,

in K2Zn,Vlo0,8,16H,0, has been deter-

mined.86

Amperometric studies

87

of thorium polyvanadates have estab-

lished the pH ranges in

which

the ortho-(3Th0,2V2O,), meta-(Th0,ZV,05),

and pyro-

(

ThO,V,O,) species are stable.

Chromium,

Molybdenum, and

Tungsten.-Reactions of the zero-valent

cyanide complexes

K,Cr(CN),

and K,Ni(

CN),

with phosphorus-, arsenic-,

and nitrogen-donors in liquid ammonia have been studied;88 complete ligand

7s

R.

J.

H.

Clark,

R.

S.

Nyholm,

and

D.

E.

Scaife,

J.

Chm.

SOC.

(A),

1966, 1296.

'*

T.

M.

Brown

and G.

S.

Newton,

Inorg.

Chem., 1966,

5,

1117.

76

G.

F.

Kokoszka,

H.

C.

Allen, and

G.

Gordon,

Inorg.

Chem., 1966, 5,91.

76

P.

A.

Kilty and

D.

Nicholls,

J.

Chem.

SOC.

(A),

1966, 1175.

77

L.

Sacconi and

U.

Canipigli,

Inorg.

Chem.,

1966,

5,

606.

M.

Zerner and

M.

Gouterman,

Inorg.

Chem.,

1966,

5,

1699.

79

G.

L.

Bertrand,

G.

W.

Stapleton,

C.

A.

Wulff, and

L.

G.

Hepler,

Inorg.

Chem.,

0.

L.

Keller and

A.

Chetliam-Strode,

Inorg.

Chem., 1966,

5,

367.

H.

Preiss,

2.

anorg.

Chem.,

1966,

346,

272.

R.

S.

Drago and

K.

W.

Whitten,

Inorg.

Chem., 1966,

5,

677.

W.

P.

Griffith and

T.

D.

Wickins,

J.

Chem.

SOC.

(A),

1966, 1087.

H.

Behrens and

A.

Muller,

2.

anorg.

Chem., 1965,

341,

124.

The ions [TaF,]- and [TaF7]2- have been identified

1966, 5, 1283.

83

I.

S.

Morozov and

A.

I.

Rlorozov,

Rzlss.

J.

Inorg.

Chem., 1966,

11,

182.

84

A.

Sabatini and

I.

Bertini,

Inorg.

Chem., 1966,

5,

204.

86

H.

T.

Evans,

Inorg.

Cliem., 1966,

5,

967.

87

R.

S.

Saxena

and

0.

P.

Sharma,

J.

Inorg.

Nudear

Chem.,

1966,

28,

195.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

192

INORGANIC

CHEMISTRY

replacement occurs in the chromium case

for

bi- and ter-dentate ligands, but

the reactions proceed best with uni-

or

bi-dentate ligands

in

the nickel case.

The

e.s.r.

spectra of the nitrosyl complexes [Cr(CN),N0]3-,

[CrNO(NH,),]

2+,

and

[CrNO(H,O),]

2+

have been interpreted,

89

and molecular orbital calcula-

tions made

for

the energy levels

of

the pentacyanonitrosyl complex.90

salts

of

the metal-cluster [W6Br816+ have been is01ated;~l the cluster

may be reduced with bromide ion to [W6Br814+.

An

incomplete description

of the preparation

of

a tungsten dihydride has appeared.92

A

peroxy-

bridged chromium compound, (H20),Cr-O-O-Cr(

H,O),,

has been isolated

93

from the reaction products of chromic acid and hydrogen peroxide. The

magnetic properties of

KCrF,,

Na,CrF,, chromium(

11)

2,2'-bipyridyl and

o-phenanthroline complexes, and

a

series of chromium(rr) double sulphates

have been studied.g4 The magnetic and spectral properties of the methoxide

compounds M(OMe),

(M

=

Cr,

Mn,

Fe, Co, Ni, Cu) and M'(OMe),

(M'

=

Ti,

Cr,

Fe) have also been inter~reted.~5 The chromium(n) and copper@)

species are said

to

be antiferromagnetic. Five-co-ordinated

compounds

have

been reported with

96

diethyldithiocarbamate

(MI1

=

Cr,

Mn,

Fe, Zn) and

tris-(2-dimethylaminoethyl)amine

(MI1

=

Cr--Zn). The chromium(rr) com-

plexes with dimethyl sulphoxide

(DMSO),

CrX2,2DMS0

(X

=1

Cl,

Br,

I),

are said to have distorted octahedral structures; the corresponding aceto-

nitrile complexes are also octahedral polymers

.97

Molybdenum phthalo-

cyanine has been prepared

98

for

the first time, and its infrared spectrum

studied.

A

convenient method for the preparation of chromium, molybdenum,

and tungsten tri-iodides

is

by reaction of iodine with the corresponding

hexacarbonyl~.~~

Chromium(=)

methoxide results

100

when tricarbonylarene-

chromium compounds are photochemically decarboxylated in methanol.

A

comprehensive study of methionine complexes of

Ag(I),

Mh,

Co, Ni,

Cu,

Zn,

Cd,

Hg, and Pb(n), and Cr, Fe,

Al,

Bi,

and Rh(m) has been reported.lol

The SCH, group

is

not co-ordinated in these complexes, but can be made

to

co-ordinate to

a

second metal, forming,

e.g.,

[Cr,Ag,(methi~nine),](ClO~)~.

With silver(I), the sulphur first co-ordinates; the

-NH2

and

-C02-

can then

L.

S.

Meriwether,

S.

D.

Robinson, and

G.

Wikson,

J.

Chem.

SOC.

(A),

1966,

1488.

go

P.

T.

Manoharan and

H.

B.

Gray,

Inorg.

Chem.,

1966,

5,

823.

9l

H.

Schlifer and

R.

Siepmann,

J.

Less-Common Metals,

1966,

11,

76.

Sa

E.

F.

Speranskaya and

T.

G.

Pokhvalitova,

Russ.

J.

Inorg.

Chem.,

1965,

10,

Q3

M.

Ardon

and

B.

Bleicher,

J.

Amer. Chem.

SOC.,

1966,

88,

858.

94

A.

Earnshaw, L.

F.

Larkworthy,

K.

C.

Patel,

K.

S.

Patel,

R.

L. Carlin, and

E.

G.

Terezakis,

J.

Chem. SOC.

(A),

1966, 511; A. Earnshaw,

L.

F.

Larkworthy, and

K.

S.

Patel,

ibid.,

p. 363;

A.

Earnshaw, L.

F.

Larkworthy, and

K.

C.

Patel,

Chem.

Comm.,

1966, 181.

Q5

R.

W.

Adams,

E.

Bishop,

R.

L.

Martin,

and

0.

Winter,

Austral.

J.

Chem.,

1966,

19,

207.

s6

J.

P. Fackler and

D.

G.

Holah,

Inorg.

Nuclear Chem.

Letters, 1966,

2,

251; M.

Ciampolini,

Chem.

Comm.,

1966,

47.

9'

D.

C.

Holah and

J.

P. Fackler,

Inorg.

Chern.,

1965,

4,

1721; 1966,

5,

479.

O8

F.

H.

Shurvell and

L.

Pinzuti,

Cunad.

J.

Chem.,

1966,

44,

125.

9s

C.

DjordjeviE,

R.

S.

Nyholm,

C.

S.

Pande, rand

M.

H.

B.

Stiddard,

J.

ChemSoc.

100

D.

A.

Brown,

D.

Cunningham,

and

W.

K.

Glass,

Chem.

Comm.,

1966, 306.

lo1

C.

A.

McAuliffe,

J.

V.

Quegliano, and

L.

M.

Vallarino,

Inorg.

Chem.,

1966,5,1996.

1303.

(A),

1966, 16.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

MABBS

AND

MACHIN: THE

TRANSITION

ELEMENTS

193

be

bonded

to

nickel

or

copper(n). The spectrum of hexa-imidazolidone-

chromium(m) has been shown to be identical with that

of

the hexa-urea

complex, whilst in the trisbiuret complex the spin-allowed

dd

bands are

shifted.lo2

It

is thought that CrCI,,ZNMe, is five-co-ordinated

loa

like the

titanium and vanadium analogues. Acetonitrile complexes [MoCl,,MeCN]

2-

and [MoC13,3MeCN]MeCN have been characterised.lo4 The tris- (cis-stilbene-

dithio1ato)M complexes

(M

=

Mo, W, Re) are trigonal prisms. Tris(to1uene-

3,4-dithiolato)- and

benzene-l,2-dithiolato-complexes

are also reported for

these metals.105 Two other extensive Papers have appeared

lo6

dealing

with dithiolato-complexes of chromium, molybdenum, and tungsten.

A

review of the oxo-compounds

of

molybdenum-(v) and

-(vI)

has

appeared.lo7 When

MOB,

reacts with,

e.g.,

PCl,, CCI,,

or

SiCI,, one

of

the

products is Mo,Cl,F,; evidence that this is

[Mo,C~,]~+[MOF,],+

is pre-

sented.lo8 In methanol solution, molybdenum(v) chloride forms

log

truns-

[(MeO),MoCl,]-; the e.s.r. and electronic spectra

of

the pyridinium salt have

been studied. In thionyl chloride, molybdenum, tungsten, and rhenium

form the oxytetrachlorides, whereas most metals form their chlorides.

The reaction mixture

W

+

WO,

+

I,

yields

W021,

when heated in

a

sealed

tube;lll WOC1, has also been studied.112 The infrared and mass spectra

of

compounds Mo0,X2 and WO,X,

(X

=

C1,

Br)

have been recorded, some of

the infrared work being on gaseous ~amples.1~3 The co-ordination chemistry

of

MoO,Cl,

and MoOC1, has also received attention.l14 The e.s.r. spectra

of

the octacyano-molybdate and -tungstate(v) ions in frozen glycerine are

consistent

115

with Archimedean antiprismatic structures, but the solid

potassium salts appear to be dodecahedral.

High pressure

(65

kbars) syntheses

116

of

alkali-metal molybdenum

bronzes have been described. The coprecipitation

of

anatase with molyb-

denum-

or

tungsten-trioxide enhances their sensitivity to photoreduction,l17

although no new compounds are formed. A series

of

heteropolyelectrolytes

[~~~m~~6~Zf~4~11~30]~1~-~-~-~~-

has been synthesised.llg The cubic

phases shrink reversibly when dehydrated

or

heated;

e.g.,

the cell edge

of

lo2

K.

K.

Cha,tterjee and

G.

B. Porter,

Inorg. Chem.,

1966,

5,

860.

lo3

G.

W.

A.

Fowles and

P.

T.

Greene,

Chem.

Comm.,

1966, 784.

1°4

P.

W.

Smith and

A.

G. Wedd,

J.

Chem.

SOC.

(A),

1966, 231.

lo5

E.

I.

Stiefel,

R.

Eisenberg,

R.

C.

Rosenberg, and

H.

B. Gray,

J.

Amer.

Chem.

lo6

G.

N.

Schrauzer and

V.

P.

Mayweg,

J.

Amer. Chem.

SOC.,

1966,

88,

3236,

G.

N.

lo'

P.

C.

H.

Mitchell,

Quart.

Rev.,

1966,

20,

103.

lo*

D.

F.

Stewart and

T.

A.

O'Donnell,

Nature,

1966,

210,

836.

log

D.

A.

McClung,

L.

R. Dalton, and

C.

H.

Brubaker,

Inorg.

Chrn.,

1966,

5,

1985.

I1O

D.

A.

Edwards

and

A.

A.

Woolf,

J.

Chem.

SOC.

(A),

1966,

91.

ll1

J.

Tillack and

P.

Eckerlin,

Angew. Chem., Internat.

Edn.,

1966,

5,

421.

Ira

G.

W.

A.

Fowles and

J.

L. Frost,

Chenz.

Comrn.,

1966, 252.

113

C.

G.

Barraclough and

J.

Stals,

Austral.

J.

Chem.,

1966,

19,

741;

T.

V.

Iorns

and

F.

E.

Stafford,

J.

Amer. Chem.

SOC.,

1966,

88,

4819.

114

M.

L.

Larson and

F.

W. Moore,

Inorg. Chem.,

1966,

5,

801.

115

B.

R.

McGarvey,

Inorg.

Chem.,

1966,

5,

476.

116

T.

A.

Bither,

J.

L. Gilson, and H.

S.

Young,

Inorg. Chem.,

1966,

5,

1559.

117

J,

A.

Chopoorian,

G.

H.

Dorion, and

F.

S.

Model,

J.

Inorg.

Nuclear

Chem.,

1966,

l1*

L.

C.

W.

Baker,

V.

S.

Baker,

K.

Eriks,

M.

T.

Pope,

M.

Shibata,

0.

W.

Rollins,

SOC.,

1966,

88,

2956.

Schrauzer,

V.

P.

Mayweg, and

W.

Heinrich,

ibid.,

p.

5174.

28,

83.

J.

H.

Fang, and

L.

L.

Koh, J.

Amer. Chem.

SOC.,

1966,

88,

2331.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

194

IN

0

R

GI.

AN10

C

H

E

MI

S

1R

Y

(~4),Na2[Ga06H,04Wl1030],15H20

falls continuously from 22-17

A

at 10"

to 21.84

A

at 47"~. Di- and tri-molybdates do not exist

llg

in

aqueous

solution, the tetramolybdate being the first species formed when molybdate

solutions are acidified. The hetero-9-molybdate ions have been

shown

to

be

stable monomers at high concentrations in solution, but they decompose

on

dilution. The pR's of the unstable acid

H,MnMo,O,,

have been deter-

mined.120 The alkaline degradation

of

metatungstate

[W1203,(

0H),l6-

is

birnolecular,l2l with an activation energy of

-9.8

kcal. mole-l.

Manganese,

Technetium,

and

Rhenium.-Rhenium(v) chloride

is

re-

duced by copper in the presence of trifluorophosphine to form Re(PF3),Cl;

Ir(PF3)41

is formed

by

oxidation

of

KIr(PF,),.

as

are

the phases Mn1+02+Mz-223+Tic04

(M3+

=

Ti,

V,

Cr).

Tetrahedral seleno-

cyanate complexes

of

Mn-Zn(rr), and octahedral Mn,Ni(n), and Fe,Y(m)

complexes are [Rh(seCN)6]3- and [M(SeCN),I2-

(M

=

Pd,

Pt)

are selenium-bonded, the remainder being nitrogen-bonded. The cyanide

complexes K4Re(CN),,3H,O and Na4Re(CN),,5H,0 are both reported

126

to

be diamagnetic. Various complexes of the bivalent ions Mn-Zn have been

prepared with pyridine, y-picoline, quinoline, 2,2'-diaminobiphenyl, and

pentamethylenetetrazine.126

The far-infrared spectra

l27

of many y-picoline

and thiourea complexes have been assigned. The 2,2',2"-terpyridyl com-

plexes of manganese, cobalt, and copper(n), (MLCl,), are isomorphous

128

with the zinc analogue and are thus five-co-ordinated; the quadridentate

ligand tris-

(2-dimethylaminoethy1)amine

forms complexes which are formu-

lated

as

[MLXIX

[M

=

M,

Fe, Zn(n);

X

=

halogen], and the terdentnte

ligand

bis-(2-dimethylaminoethyl)methylamine

also forms five-co-ordinated

complexes, [MLX,].129

No new meta.1-cluster compounds have been reported

for

these metals;

however,

a

number of structural determinations have appeared, and some

reactions

of

known specie8 studied.

The structures of (Ph,As),[Re3Clll] and

Cs2[Re,Brll] are based

l30

on that of Re3Cl12, but one terminal, in-plane

halogen atom is absent.

Metal-metal bond lengths to the unique rhenium are

shorter than the remaining bond (2.43 cf.

2.49,

and 2.44 cf.

2-48

A

in the

Both

tc-

and

p-forms

of

manganese titanate are ferrimagnetic

lLg

0.

Glemser and

W.

Holtje,

Angew.

Chem.,

Internat.

Edn.,

1966,

5,

736.

lZo

L.

C.

W.

Baker and

T.

J.

R.

Weakley,

J.

Inorg. Nuclear Chem.,

1966,

28,

447.

121

0.

Glemser,

W.

Holznagel, and

W.

Holtje,

2.

anorg. Chem.,

1966,

342,

75.

122

T.

Kruck,

A.

Englemann, and W. Lang,

Chern. Ber.,

1966,99,

2473.

lZ3

P.

Hagenmuller, Ch. Guillaud,

A.

Lecerf,

M.

Rault, and G. Villers,

BulZ.

SOC.

chim France,

1966, 2589.

124

J.

L.

Burmeister

and

L.

E.

Williams,

Inorg. Chem.,

1966,

5,

1113;

D.

Forster

and

D.

M.

L.

Goodgame,

ibid.,

1965,

4,

1712.

lZ6

S.

Sen,

2.

anorg. Chem.,

1965,

340,

82.

lZ6

D.

H. Brown,

R.

H.

Nuttall,

J.

McAvoy, and

D.

W.

A.

Sharp,

J.

Chem.

SOC.

(A),

1966,

892;

F.

Hein and W. Jehn,

2.

anorg. Chem.,

1965,341,244;

F.

M.

D'Itri and

A.

I.

Popov,

Inorg. Chem.,

1966,

5,

1670.

12'

M.

Goodgame and

P.

J.

Hayward,

J.

Chem. SOC.

(A),

1966,

632;

C.

D.

Flint

and

M.

Goodgame,

ibid.,

p.

744.

12*

C.

M.

Harris,

T.

N.

Lockyer, and

N.

C.

Stephenson,

Austral.

J.

Chem.,

1966,

19,

1741.

129

M.

Ciampolini and G.

P.

Speroni,

Inorg. Chem.,

1966,

5,

45;

M.

Ciampohi and

N.

Nardi,

ibid.,

p.

1150.

130

B.

R.

Penfold and

W.

T.

Robinson,

Iwg.

Chem.,

1966,

5,

1758;

M.

Elder

and

B.

R.

Penfold,

ibid.,

p.

1763.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

MABBS

AND

MACHIN:

THE

TRANSITION

ELEMENTS

195

chloride and bromide, respectively). The structure

of

Re3Br,(AsO,),,3DMSO

also

retains the triangle

of

rhenium atoms

;I31

three oxygens

of

the arsenate

are bonded to the triangle of rheniums, one above and one below the plane.

Reactions

132

of

the [Re,X,I2- ion yield ReX,(Ph,P),, [Re(diphosphine)Cl,],

carboxylates Re,(O,CR),X,, and 2,5-dithiahexane forms Re,Cl,L,.

The

structure

of

the last complex is a dimer [ReCl,][ReL,Cl]; the ReC1, and

ReS, planes are not eclipsed, and thus not &bonded. Molten dimethyl

sulphone does not react

133

with Re,Cl,, but addition

of

chloride ion yields

[Re,C1,I2-. In fused Li-KC1 eutectic, this reaction yields rhenium(0) and

[ReCl,]

,-.

Re,Cl, reacts

134

with 2,2'-bipyridyl, o-phenanthroline, diphos-

phines, and 2,5-dithiahexane,

to

yield complexes Re,Cl,L,.,

for

all except

the o-phenanthroline

;

their spectra suggest that the trimeric structure

is

retained in the adducts.

Re3C1,L, species are formed with unidentate

ligands,

L.

The trigonal prismatic co-ordination

of

tris-(cis-lY2-diphenylethane-l

,2-

dithio1ato)rhenium has been confirmed.135 Other

trismaleonitriledithiolate

complexes

of

manganese, iron, molybdenum, and tungsten are suggested

as

having this structure.

The spectra of tris-dithiocarbamate, 2,2'-bipyridyl, and acetylacetonato-

complexes of manganese(m) have been assigned.13' The

5Bg

+

5T2g

transition occurs at

N

20,000 cm.-l, t.he lower energy (5000--15,000 cm.-l)

band being attributed to a charge-transfer process. Pentachloromangan-

ate(=) complexes are formed

138

when concentrated hydrochloric acid

reacts with potassium pernianganate in the presence of,

e.g.,

2,2'-bipyridyl ;

at lower acidity, MnLCl,,H,O is formed, as well

as

MnLCl,. The thermal

decomposition

of

pyridine (py) adducts ReBr3,2py and [ReO,py,]Br has been

re~0rted.l~~

The spectra of K,ReCl, in molten dimethyl sulphone, diethyl-

amine hydrochloride, or Li-KC1 eutectic reveal

a,

larger splitting

l40

of

the

ligand-field bands in the latter solvent. Crystals of technetium(Iv) chloride

contain zig-zag chains

of

octahedra sharing

two

edges.141 This compound

forms

142

octahedral adducts TcC14L2

(L

=

Ph,P

or

Ph3As), TcCl,bipyridyl,

and [TcCl,( bipyridyl),]Cl,.

Bisdiphenylphosphinoethane

forms the tervalent

complex [TcCl, (diphos)

JC1.

The physical properties

of

compounds MITcF,

(MI

=

Na,

K,

Rb,

Cs)

have been studied.la3

A square-pyramidal structure is proposed

14,

for

131

F.

A. Cotton and

S.

J.

Lippard,

J.

Amer. Chem.

SOC.,

1986,

88,

1882.

132

F.

A.

Cotton,

N.

F.

Curtis, and W.

R.

Robinson,

Inorg. Chem.,

1935,

4,

1696;

F.

A.

Cotton,

C.

Oldham, and

W.

R.

Robinson,

ibid.,

1966,

5,

1798;

M.

J.

Bennett,

F.

A.

Cotton, and R. A. Walton,

J.

Amer.

Chem. SOC.,

1906,

88,

3866.

133

R.

A.

Bailey and

J.

A.

McIntyre,

Inorg. Chem.,

1966,

5,

1940.

134

F.

A.

Cotton and

R.

A. Walton,

Inorg. Chem.,

1966,

5,

1802.

135

R.

Eisenberg and

J.

A.

Ibers,

Inorg. Chem.,

1966,

5,

411.

136

M.

Gerloch,

S.

F.

A.

Kettle,

J.

Locke, and

J.

A.

McCleverty,

Chem. Comm.,

13'

R.

Dingle,

Acta

Chem. Scand.,

1966,

5,

33.

138

H.

A.

Goodwin and

R.

N.

Sylva,

Austral.

J.

Chem.,

1965,

18,

1743.

13D

V.

G. Tronev and

R.

A.

Dovlyatskina,

Russ.

J.

Inorg. Chem.,

1965,

10,

1230.

140

R.

A.

Bailey and

J.

A.

McIntyre,

Inorg.

Chent.,

1966,

5,

964.

141

M. Elder and

B.

R.

Penfold,

Inorg. Chem.,

1966,

5,

1197.

142

J.

E.

Fergusson and

5.

H. Hickford,

J.

Inorg. Nuctear Chem.,

1966,

28,

2293.

143

D.

Hugill and

R.

D.

Peacock,

J.

Chem.

SOC.

(A),

1966, 1339.

144

F.

A. Cotton and

S.

J.

Lippard,

Inorg. Chem.,

1966,

5,

9.

1966, 29.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

196

INORGANIC

CHEMISTRY

the [ReX,O]- ion

(X

=

C1,

Br,

I).

K3&O,

is stable

to

at

least

800°c,

but

K2Mn04

decomposes reversibly at

MO-680 OC.

The initial decomposi-

tion products on heating

KMnO,

are

K,MnO,,

&&O,,

and

MnO,.

In

a

study

of

the oxidising power of metal hexafl~orides,l~~

it

was shown that

ReF6 oxidises nitric oxide, yielding NO+ReF6; with

NOE',

(NO),ReF, was

formed. The chemistry

of

rhenium-(Iv) and

-(v)

oxychlorides has been

investigated.147

In

alkaline solutions, B+[ReOCZ,]

(B+

=

Ph,As,

Et,N,

or

acridinium) disproportionates to rhenium-(Iv) and

-(

vr1).14g Rhenium

hydride-phosphine complexes are harder to prepare than those

of

other

metals; compounds ReH,(PR,),, [ReH,(PR,),],, and ReH5(PR3), have been

is01ated.l~~ Barium and strontium nitrides react with rhenium to

form

l50

the ternary species M,Re,N,,

(M

=

Ba,

Sr).

Osmium only forms the barium

compound.

A

thermally unstable compound Sr,,Re5N,, was also detected.

Iron,

Ruthenium,

and

Osmium.-Dinitrosyl

iron,

cobalt, and nickel

halides react with either tetraphenyldiphosphine

or

diarsine to give the

following

(NO)2Fe(Ph2PPPh2)a, [(NO),Fe(Ph,PPPh,)J,, [X(NO),BeEPh,],,

[

(NO),FeEPh,],,

[X(

NO),CoPh,EEPh,Co(

NO),X],,

[

(Ph,PPPh,) (NO)NiX),,

and [X(NO)NiAsPh,],

(E

=

P

or

As;

X

=

halide).151 With iron and cobalt

nitrosylcarbonyls and 1,2-bis(

dipheny1phosphino)ethane

(

=

diphos) the

compounds [Fe(

NO),(

diphos)]

,

[Co(NO)

(CO)

(diphos)],

[&(NO)(

C0),l2(

diphos), and

[(NO),(

CO)Fe(

diphos)Co(NO)

(CO),]

were

isolated.

l52

The complexes [FeS,C,(CF,),], [FeS,C,Ph,], and [CoS,C,Ph,] have been

reported to be metal-sulphur bridged dimers with structures analogous to

that of [Co,S4C4(

CF3),],.

Their electronic properties and reactions with

phosphines and Fe(

CO),

were also given.153

~S,C,(CF,),],

(M

=

Fe

or

Co) shows the following one-electron reduction

processes

:

The polarography

of

[MS4C4(CF,)&

+

[MS-iC,(CFd4]2-

*

CMS&I(CFJ~I-

The isolation and magnetic properties

of

the mononegabive dimers, and

of

similar

rnaleonitrile-dithiolate

(mnt2-) and toluene-3,4-dithiolate (tdt2-)

compounds were also described.154 Similar polarographic studies indicated

the existence of [M(tdt)J2- and [M(tdt),]- complexes

(M

=

Fe,

Co,

Ni, Pt,

Cu,

Au),

but

only the [M(tdt),]-

(M

=

Fe,

Co,

Au) compounds could be

isolated.155 The preparations and magnetic properties

of

some complexes

145

H. Peters,

K.

H.

Radeka, and

L.

Till,

2.

anorg.

Chm.,

1966,346,l.

146

N.

Bartlett,

S.

P.

Beaton, and

N.

K.

Jha,

Chem.

Comm.,

1966, 168.

14'

G.

Rouschias

and

G.

Wilkinson,

J.

Chern.

SOC.

(A),

1966, 465;

D.

E.

Grove and

l48

B.

J.

Brisdon and

D.

A. Edwards,

Chem.

Comm.,

1966,

278.

140

J.

matt and

R.

S.

Coffey,

Chem.

Comm.,

1966,

545.

l50

F.

K.

Patterson and

R.

Ward,

Inorg.

Chem.,

1966,

5,

1312.

151

W.

Hieber and

R.

Kummer,

2.

anorg.

Chem.,

1966,

344,

292.

152

R.

J.

Mawby,

D.

Morris,

E.

M.

Thorsteinson, and

F.

Basolo,

Inorg.

Chem.,

1966,

153

G.

N.

Schrauzer.

V.

P.

Mayweg,

H.

W. Finck, and W. Heinrich,

J.

Amer.

Chem.

G.

Wilkinson,

&id.,

p.

1224.

5,

27.

1-

SOC.,

1966,

88,

4604.

154

A.

R.

Balch and

R.

H.

Holm,

Chem.

Cornm.,

1966, 552.

155

R.

Williams,

E.

Billig,

J.

H.

Waters,

and

H.

B.

Gray,

J.

Amer.

Chem.

SOC.,

1966,

88,

43.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

MABBS AND

MACHIN:

THE

TRANSITION

ELEMENTS

197

of

the types [Fe (NO)S,C,Ph,]

-,

[Fe( NO)S,C,Ph,]

-,

[Fe(NO)S,C,Ph,]o, and

[Fe(NO)S,C,Ph,],- have also been reported.ls6

A

series of complexes

of

the type Fe phen,X,

(X

=

C1,

Br,

NCS,

NCSe,

OCN,

N,,

HCO,,

CH,CO,) have been prepared and shown to be high-spin

with

peff

in

the range

5-1-5.3

B.M.l57 The magnetism and electronic spectra

of

the complexes with

X

=

C1,

Br, and

N3

have been interpreted on the basis

of molecular orbital models based

on

C,,

of

DPh

syrnmetrie~.l5~

When

X

=

NCS or NCSe the magnetic behaviour has been interpreted in terms

of

a

5T,

+

lAl

eq~ilibrium.l5~ The magnetic susceptibility data over the

temperature range

77-300"~

and the Mossbauer spectral data of the com-

plexes [Fe phen,X]nH,O

(X

=

oxalato, n

=

5;

or

X

=

malonato,

n

=

7)

have been discussed in terms

of

a spin-triplet ground state.160 The relation-

ship between

peff

and the Mossbauer quadrapole splitting parameter,

dEQ,

for

the complexes Fe py4X,

(X

=

Cl,

Br,

I,

NCS,

OCN)

has been discussed

with the assumption that they are tetragonally distorted octahedral com-

plexes.161

The Mossbauer spectra

of

iron(@

phthalocyaninedipyridine,162

iron-(II) and

-(m)

substituted salicylaldo~irne,l6~ nucleotide, nucleic acids,

and

EDTA

complexes

164

have been discussed in terms

of

the modes

of

metal-ligand bonding.

Similar Mossbauer spectral studies coupled with

infrared and electronic spectra have been used to distinguish [FeCl,]- from

[FeC1,I3- ions,165 and to discuss the structures

of

Fe phen,X, and

[Fephen,]X, (X

=

Cl, Br, NCS, OCN, HC0,).166

The changes, due to pressure, in the electronic absorption spectrum

of

Gillespite, BaFeSi,O,,, have been interpreted

in

terms of changes in metal-

ligand distances causing spin-pairing.

167

The absorption spectra of the

complexes

[M

bipy3]Br,,6H,0,

[M

bipy3]S0,,7H20

(M

=

Fe, Ru, Co,

Ni,

Cu), [FeL,X,]

(L

=

isoqinoline,

/I-

and y-picoline, 4-cyanopyridine,

3,5-

dichloropyridine;

X

=

halide),

[M

bipy2X2],,

[M

bipy2X,]X

(M

=

Fe,

Ru,

0s;

X

=

C1,

Br,

I),

and [Ru(diamine),]X,

(X

Br,

I,

SCN,

$S203)

have been

reported and discussed in terms

of

deviations from octahedral symmetry,

metal-ligand bonding, and ligand-field parameters.16* Further studies of

the optical spectra

of

[Fe(CN),NOI2- have led to the suggestion

of

the

156

J.

Locke,

J.

A.

McCleverty,

E.

J.

Wharton, and

C.

J.

Winscorn,

Chem. Comm.,

15'

K. Madeja,

W.

Wilke, and

S.

Schmidt,

2.

anorg.

Chem.,

1966,

346,

306.

158

P.

Spacu

and

C.

Lepadatu,

J.

Amer. Chem.

SOC.,

1966,

88,

3221.

159

E.

Konig and

K.

Madeja,

Chem. Comm.,

1966, 61.

160

E.

Konig and K. Madeja,

J.

Amer. Chem.

SOC.,

1966,

88,

4528.

161

R.

M.

Golding,

K.

F.

Mok, and

J.

F.

Duncan,

Inorg.

Chem.,

1966,

5,

774.

162

A.

Hudson and H.

J.

Whitfield,

Chm.

Comm.,

1966, 606.

163

K.

Burger,

L.

Korecz,

I.

B.

A.

Manuaba, and

I?.

Mag,

J.

Inorg.

Nuclear Chem.,

lB4

I.

N.

Rabinowitz,

F.

F.

Davis, and

R.

H.

Herber,

J.

Amer. Chem.

SOC.,

1966,

G.

M.

Bancroft,

A.

G.

Maddock, W.

K.

Ong, and R.

H.

Prince,

J.

Chem.

SOC.

(A),

1966, 677.

1966,

28,

1673.

88,

4346.

1966, 723.

166

J.

F. Duncan and

K.

F.

Mok,

J.

Chem.

SOC.

(A),

1966, 1493.

16'

R.

G.

J.

Strens,

Chem. Cornm.,

1966, 777.

168

D.

35.

L.

Goodgame,

M.

Goodgame,

M.

A.

Hitchman, and

M.

J.

Weeks,

Inorg.

Chem.,

1966,

5,

635;

R.

A.

Palmer and

T.

S.

Piper,

ibid.,

p.

864;

J.

E.

Fergusson and

G.

M.

Harris,

J.

Chem.

SOC.

(A),

1966, 1293;

H.

H.

Schmidtke and D. Garthoff,

Hdv.

Chim.

Acta,

1966,

49,

2039.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

198

INORGANIC CHEMISTRY

following revised energy-level scheme

:I69

ZZ,

YZ

<

XY

<

n*NO

<

Z'

-

y8

<

Z'

The infrared spectra of complexes

MX2,2NH,

(M

=

Fe,

Co,

Ni,

Cu,

Zn,

Cd, Hg, Pd, Pt;

X

=

C1,

Br,

I)

in the range 4000-200 cm.-l have been

reported, and the

M-N

and M-halogen stretching frequencies discussed in

relation to the structures of the complexes.lV0 In the complexes

[Ru,(OCOR),Cl] (R

=

Me,

Et,

Pr"),

which contain ruthenium in the for-

mal oxidation states

II

and

m,

the room-temperature magnetic moments

suggest that some of the ruthenium is in the spin-free state.lV1 The magnetic

moments and electronic spectra of

a

number

of

iron(=), cobalt(@, nickel(n),

copper(=), and zinc(n) Schiff base and other nitrogen-donor complexes have

been used to suggest their structures.172

The magnetic susceptibility data

for

several spin-paired iron(m) and

ruthenium(m) complexes,173 and the near-infrared spectrum

of

Os(acac),l74

have been interpreted in terms

of

a

,TZg

ground state which has been per-

turbed by spin-orbit coupling and an

axial

ligand-field component. The

preparation, magnetic properties, and structures of

a

binuclear and

a

mono-

nuclear form of [Fe(salen)Cl] have been described.lV6 In the diethyldithio-

carbamate complex, [Fe(S,CNEt,),Cl], magnetic susceptibility measurements

and an X-ray structure determination have shown

it

to contain five-

co-ordinate (essentially square-pyramidal) iron(@ with

a

spin quartet

ground-state.lV6 The Mossbauer and proton n.m.r. spectra of several other

iron(m) dithiocarbamate complexes have been interpreted in terms of the

symmetry

of

the ligand field and iron d-electron delocalisation.177 The

magnetic exchange interactions

in

trimeric n-alkoxide complexes, [Fe,(

OR),],

have been interpreted in terms

of

a

dipolar coupling scheme

for

a

triangular

cluster

of

spin-free iron(m) ions

(8

=

5/2),178

whilst in the complexes

[Fe,O(phen),]X,

(X

=

C1,

NO,)

each interacting

iron

has been assumed to

have

a

spin-paired ground state

(8

=

+).l79

Magnetic susceptibility, electrical conductivity, and infrared spectral

measurements have been used

to

deduce that in the complexes [FeBX,]Y

(X

=

C1,

Br,

I,

NCS; Y

=

ClO,,

BF,, NCS;

B

=

the quinquedentate

2,13-dimethyl-3,6,9,12,18-penta-azabicyclo[

12,3,

lloctadeca-

1

(

18)

,2,12,14,16-

160

H.

B.

Gray,

P.

T.

Manoharan,

J.

Pearlman, and R. F. Riley,

Chem.

Comm.,

1966, 62.

l70

R.

J.

H.

Clark and

C.

S.

William,

J.

Chem. SOC.

(A),

1966, 1425.

171

T.

A. Stephenson and

G.

Wilkinson,

J.

Inorg.

Nuclear

Chem.,

1966,

28,

2285.

172

J.

R.

Allan,

D.

H.

Brown,

R.

H.

Nuttall, and

D.

W. A. Sharp,

J.

Chem.

SOC.

(A),

1966, 1031;

L.

F.

Lindsay,

S.

E.

Livingstone,

T.

N.

Lockyer,

and

N.

C.

Stephenson,

Austral.

J.

Chem.,

1966,

19,

1165;

W.

R. McClellan and

R.

E.

Benson,

J.

Amer.

Chem.

SOC.,

1966,

88,

5165;

M.

A.

Robinson and

T.

J.

Hurley,

Inorg.

Chem.,

1965,

4,

1716;

H.

M. Fisher and R.

C.

Stoufer,

Inorg. Chem.,

1966,

5,

1172;

M.

A.

Robinson and

T.

J.

Hurley,

J.

Inorg. Nuclear

Chem., 1966,

28,

1747.

173

B.

N.

Figgis,

J.

Lewis, F.

E.

Mabbs and

G.

A.

Webb,

J.

Chem. SOC.

(A),

1966,422.

174

R. Dingle,

J.

Mol. Spectroscopy,

1965, 18, 276.

M.

Gerloch,

J.

Lewis,

F.

E.

Mabbs, and A. Richards,

Nature,

1966,

212,

809.

176

B.

F.

Hoskins, R.

L.

Martin, and A.

H.

White,

Nature,

1966,

211,

627.

177

E.

Frank and

C.

R. Abeledo,

Inorg.

Chem., 1966,

5,

1453;

R.

M. Golding,

W.

C.

Tennant, C. R. Kanekar, R.

L.

Martin, and A.

H.

White,

J.

Chem.

Phys.,

1966,

45,

2688;

R.

M. Golding and H.

J.

Whitfield,

Trans.

Paraday

SOC.,

1966,

62,

1713.

178

R.

W.

Adam,

C.

G.

Barraclough,

R.

L.

Martin, and

G.

Winter,

Inorg.

Chem.,

1966,

5,

346.

179

I,.

N.

Mulay and

N.

L.

Hofmann,

Inorg.

Nuclear

Chem.

Letters,

1966,

2,

189.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

BTABBS

AND

MACHIN: THE TRANSITION ELEMENTS

199

pentaene} the iron is seven-co-ordinate with the group

Y

unco-ordinated.ls*

From infrared and Raman spectral studies on

[M(NH3)6]3+

and [M(ND3)6]3f,

the skeletal vibrational modes have been assigned.ls1 On the basis

of

their

Faraday rotations the

24,100

and

32,900

cm.-l charge-transfer bands

of

K,Fe(CN), have been assigned to the

2T20

-+

2Tlzc

and

2Tzg

-+

2T2u

transi-

tions, respectively.ls2

Magnetic susceptibility and infrared spectral measurements on the com-

plexes [Fe(diars),X,](BF,),

(X

=

C1,

Br)

have been interpreted in terms

of

a

tetragonally distorted spin-paired iron(

IV)

complex with

trans-

halides.

83

The magnetic interactions in the complexes MRuO,, Sr,RuO,, and

(BaBi6 Sr1/B)R~03

(M

=

Sr,

Ca, Ba) have been discussed in relation to the

structures

of

these cornple~es.~~4 In the solid state,

(NH,),[oS,o

Cll,]H20 is diamagnetic, but in aqueous solution paramag-

netism corresponding to four unpaired electrons has been observed. This

behaviour in solution was interpreted on the basis

of

a dimer

.c-

monomer

equilibrium.185 The preparation and characterisation

of

OsF, has been

described.

186

The gas-phase infrared spectrum of

OsO,

has been interpreted

on the basis

of

a

normal co-ordinate analysis.ls7

Cobalt,

Rhodium,

and

Iridium.-Refluxing

[

(Ph,P),RhCl] with carbon

disulphide has led to the isolation

of

trans-[

(Ph,P),Rh(CS)Cl] which in turn

can be oxidised with chlorine to [(Ph3P),Rh(CS)Cl,].18s Rhodium-boron

bonds are reported to occur in compounds of the type [L,Rh(CO)X*BY,]

(X

=

Y

=

C1,

Br;

L

=

Ph3P

or

Ph,As).lsS The reaction between

[Co(CN)J3-

and sulphur dioxide or stannous chloride has led to the isolation

of

the complexes [(NC),Co-A-Co(CN),]6-

(A

=

SO,

or

SnCl,), which contain

either Co-S-Co

or

Co-Sn-Co linkages.190 Sulphur dioxide has been shown

to addreversiblyto compounds

of

the type [MCl(CO)(Ph,P),]

(M

=

Rh, Ir).lgl

A number

of

hydrido- and deuterio-iridium complexes, containing triphenyl-

phosphine and carbon monoxide as other ligands, have been prepared and

characterised using infrared and n.m.r. spectroscopy.

lg2

Complexes

of

the

type [M(dp),]X [dp

=

C2H,(PPh,),;

M

=

Co,

X

=

ClO,;

M

=

Ir,

X

=

C1,

Br,

I,

ClO,,

BPh,] have been shown to add hydrogen, hydrogen halides,

carbon monoxide, and sulphur dioxide. The iridium complexes add mole-

cular oxygen reversibly, whereas the cobalt complex

was

oxidised to

cobalt

(

II)

.

l9

3

S.

M.

Xelson,

P.

Bryan, and

I).

H.

Busch,

Chem.

Comm.,

1966, 641.

W.

P.

Griffith,

J.

Chem.

SOC.

(A),

1966, 899.

lS2

P.

J.

Stephens,

Inorg.

Cltem.,

1965,

4,

1690.

lS3

G.

S.

F.

Hazeldean,

R.

S.

Nyholm, and

R.

V.

Parish,

J.

Chem.

SOC.

(A),

1966, 162.

la4

A.

Callaghan,

C.

W.

Moeller, and

R.

Ward,

Inorg.

Chem.,

1966,

5,

1572.

lS6

B.

Jesowska-Trezebiatowska,

J.

Hanuza, and

W.

Wojciechowski,

J.

Inorg.

lS6

0.

Glemser,

H.

W.

Roesky,

K.-H.

Hellberg, and

H.-U.

Werther,

Chew

Ber.,

Nmlear

Chem., 1966,

28,

2701.

1966,

99,

2652.

I.

W.

Levin

and

S.

Abramowitz,

Inorg.

Chem.,

1966,

5,

2025.

M.

C.

Baird and

G.

Wilkinson,

Chem.

Comm.,

1966, 267.

P.

Powell and

H.

Noth,

Chem.

Comm.,

1966, 637.

lS0

A.

A. VEek and

F.

Basolo,

Inorg.

Clzem.,

1966,

5,

156.

lgl

L.

Vaska and

S.

S.

Bath,

J.

Amer. Chent.

Soc.,

1966,

88,

133.

lS2

L.

Vaska,

Chem.

Comm.,

1966, 614;

R.

C.

Taylor,

J.

F.

Young, and

G.

Wilkinson,

lv8

A.

Sacco,

M.

Rossi,

and

C.

F.

Nobile,

Chem.

Comm.,

1966, 589.

Inorg.

Chem.,

1966,

5,

20.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

200

INORGANIC

CHEMISTRY

The existence of an electron-transfer series of the type

[MD,]*

(D

=

di-

anion

of

o-phenylenediamine;

M

=

Co,

Ni, Pd, Pt;

x

=

-2,

-l,O,

3-1,

+2)

has been demonstrated, and some of the members

of

the series is01ated.l~~

A

series

of

complexes

[(n-C,Hg)4N][M(S,C6X,Y2),]

(M

=

Co, Ni,

Cu;

X

=

Y

=

H,

Me, Cl, or X

=

H,

Y

=

Me) have been isolated, and their

spectral and magnetic properties shown to be consistent with

a

molecular

orbital energy scheme in which the highest filled orbitals are largely ligand

in cornpo~ition.~~5

The complex [Co(paphy)Cl,] [paphy

=

1,3-bis-(2-pyridy1)-2,3-diazaprop-

l-ene] has been isolated as

a-

and /3-modifications.

An

X-ray structure

determination has shown the 8-form to be a five-co-ordinate monomer with

essentially square-pyramidal geometry, whereas magnetic and spectral data

for

the cc-form are consistent with an octahedral str~cture.~~6 The ligand

tris-(2-dimethylaminoethyl)amine

(tren Me) forms high-spin five-co-ordinate

complexes

of

the type [M(tren

Me)X]X

[M

=

Co(n),

Ni(n),

Cu(rr); X

=

Cl,

Br,

I,

NO,,

ClO,]

which are thought to have trigonal-bipyramidal struc-

ture~.~~~ The proton nuclear magnetic resonance contact shifts

for

com-

plexes [CoL,X,]

[L

=

py, (Me,N),PO;

X

=

C1,

Br,

I,

NCS] and

[ML,]

M

=

Co, Ni;

L

=

isoquinoline 2-oxide, quinoline l-oxide)

have

been inter-

preted

in

terms

of

unpaired electron spin delocalisation through

cr-

and/or

n-bonding mechanisms.lg8 Similar contact shift measurements for the

complexes [M(acac),]- and [M(acac),(pyNO),]

(M

=

Co,

Ni) have been inter-

preted in terms

of

electron delocalisation. The results were also used to

estimate the magnetic anisotropy of

[Co(acac),]-

(KII

-

KL

=

-4280

x

c.g.s.u. mole-l) and the

M-0-N

angle (114-125') in the pyN0 complexes.199

The structures of complexes

of

the types

[Co

L6]&

,O0

(L

=

hydrazine,

NN'-dimethylacetamide, di-2-pyridylamine, 3-substituted urea

;

X

=

halide,

C104,

NO,)

and [CoL,X,j

,01

(L

=

NN-dimethylthioacetamide,

4,4'-diethoxy-

carbonyl-

3

,

3'

,5,5'-

t

e trameth yldip yrr ome

t

hane

,

substi-

tuted pyridines,

a-benzylene-2,1-benzimidazole,

substituted thiourea

;

X

=

halide, NCS,

NO,)

have been inferred from magnetic and spectral measure-

194

A.

L. Balch and

R.

H.

Holm,

J.

Arner. Chem.

SOC.,

1966,

88,

5201.

lS5

M.

J.

Baker-Hawkes,

E.

Billig, and

H.

B.

Gray,

J.

Amer. Chem.

SOC.,

1966,

88,

196

I.

G.

Dance, M. Gerloch,

J.

Lewis, F.

S.

Stephens, and F. Lions,

Nutzcre,

1966,

197

M.

Ciampolini and

N.

Nardi,

Inorg.

Chern.,

1966,

5,

41.

198R.

W.

Kluiber and

W.

Dew. Horrocks,

jun.,

J.

Amer. Chem.

SOC.,

1966,

88,

1399;

B.

€3.

Wayland and R. S. Drago,

ibid.,

p. 4597.

lS9

R. W. Kluiber and

W.

Dew. Horrocks, jun.,

J.

Amer. Chern.

SOC.,

1965,

87,

5350; W. Dew. Horrocks,

jun.,

R.

H.

Fischer,

J.

R.

Hutchinson, and G.

N.

LaMar,

ibid.,

1966,

88,

2436.

ZOOM.

Goodgame,

J.

Chem.

SOC.

(A),

1966, 63; D. Nicholls,

M.

Rowley, and

R.

Swindells,

ibid.,

p. 950;

P.

S.

Gentile and

T.

A.

Shankoff,

J.

Inorg.

Nuclear Chem.,

1966,

28,

1283;

S.

K.

Madan and

A.

M.

Donohue,

ibid.,

p.

1617;

J.

A.

Costamagna and

R. Levitus,

ibid.,

p. 2685;

B. B.

Wayland,

R.

J.

Fitzgerald, and

R.

S. Drago,

J.

Amer.

Chem.

Xoc.,

1966,

88,

4600.

201

J.

deO. Cabral,

H.

C.

A.

King, S.

M.

Nelson,

T.

M.

Shepherd, and

E.

Koros,

J,

Chem.

SOC.

(A),

1966, 1348;

J.

Ferguson and

B.

0.

West,

ibid.,

p.

1569;

S.

K. Madan

and

D.

Mueller,

J.

Inorg.

Nuclear

Chem.,

1966,

28,

177;

S.

K.

Madan and

C.

Goldstein,

ibid.,

p. 1251;

G.

Yagupsky, R.

H.

Negrotti, and R. Levitus,

J.

Inorg.

Nuclear

Chaem.,

1965,27,2603;

M.

S. Elder,

G.

A.

Melson, and

D.

H.

Busch,

Incwg.

Chem.,

1966,5,74.

E

-

thio capr ola

c

t

am,

4870.

210,

295.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

MABBS AND

MACHIN: THE

TRANSITION

ELEMENTS

201

ments. The formation

of

octahedral cobalt(=) and tetrahedral cobalt(n)

and copper

(11)

azido-complexes

in

methyl cyanide, dimethyl sulphoxide,

and trimethyl phosphate has been demonstrated.

202

The infrared spectra

of

(Et4N),[Co(N,),] and (Et,N),[Zn(N,),]

in

the solid state indicata

a

non-

linear

M-N-N

linkage.203

From

similar studies on [M(~U)~X,]

(M

=

Go, Zn,

Cd;

X

=

C1,

Br,

I;

tu

=

thiourea), ~i(tu),]X, (X

=

Br-,

NO,-), and

[Ni(

tu),Cl,], metal-sulphur and metal-halogen stretching frequencies have

been identified.204

A

study

of

the spectral and magnetic properties

of

solutions

of

bis-(8-keto-amino)cobalt

(n)

complexes show that a planar

(S

=

8)

+

tetrahedral

(8

=

3/2)

configurational equilibrium exists.205

The electronic spectra

of

the complexes [Co(amine),X,]

(X

=

C1,

Br,

I,

NCS,

NCSe) are virtually independent

of

the amine, except when they con-

tain a-substituted pyridines which decrease the supposed

4B2

-+

4A,

transi-

tion by as much as

1000

cm.-1.206 Although the free ligand dithioacetyl-

acetone is not known,

it

has been stabilised in the complexes [M(SacSac),]

[M

=

CO(II),

Ni(rr),

Pd(n),

Pt(n)

;

SacSac

=

dithioacetyla~etonatoo].~~7

A

tetrameric complex, [co,o( OCOCMe,)6], for which the magnetic moment

indicates magnetic exchange interactions between the cobalt atoms, has

been isolated.

208

The absolute configurations

of

the complexes

a-(

+)-tris-L-alaninato-

Co(m)

,09

and

(

+

)-cis-dinitrobis-(

-

)-propylenediamine-Co(m)

chloride

have been determined by single-crystal X-ray determinations and correlated

with their circular dichroism spectra. The circular dichroism, optical,

and optical rotatory dispersion spectra of

a

number

of

cobalt

(111)

ethylenedi-

amine, propylenediamine, cyclohexanediamine, and NNN'N'-tetrakis-(Z-

aminoethy1)- 1,2-diaminoethane complexes

211

and

of

[CoX,I2-

(X

=

C1,

Br,

I)

have been reported and discussed in terms of the ligand-field

symmetries and configurational effects. The isolation

of

geometrical isomers

of

a

number

of

tris- bidentate and hexa-co-ordinated mixed ligand cobalt

(m)

complexes have been reported, and in some cases their electronic spectra are

discussed.

21

203

V.

Gutmann and

0.

Leitmann,

Monalsh.,

1966,

9'9,

926.

203

D.

Forster and

W.

Dew.

Horrocks,

jun.,

Inorg.

Chem.,

1966,

5,

1510.

204

C.

D. Flint and

M.

Goodgame,

J.

Chem.

SOC.

(A),

1966, 744.

205

G.

W.

Everett, jun., and

R.

H.

Holm,

J.

Amer. Chem.

SOC.,

1966,

88, 2442.

206

A.

B.

P.

Lever and

S.

M.

Nelson,

J.

Chem.

SOC.

(A),

1966, 859.

207

R.

L. Martin and

I.

M.

Stewart,

Nature,

1966,

210,

522.

208

A.

B.

Blake,

Chem. Comm.,

1966, 569.

209

M.

G. B. Drew,

J.

H.

Dunlop,

R.

D.

Gillard, and

D.

Rogers,

Inorg.

Chem.,

1966,

5,

42.

210

G.

A.

Barclay,

E.

Goldschmied,

N.

C.

Stephenson, and A.

M.

Sargeson,

Chem.

Cornm.,

1966, 540.

211

B.

E.

Douglas,

Inorg.

Chem.,

1965,

4,

1813;

H.

L.

Smith

and

B.

E.

Douglas,

Inorg.

Chem.,

1966,

5,

784;

R.

S.

Treptow,

ibid.,

p.

1593;

A.

J.

McCaffery,

S.

F.

Mason,

and

B.

J.

Norman,

Chem. Comm.,

1966, 661;

J.

R.

Gollogly and

C.

J.

Hawkins,

ibid.,

p.

873;

S.

F. Mason and

B.

J.

Norman,

J.

Chem.

Sbc.

(A),

1966, 307;

C.

J.

Hawkins,

E.

Larsen, and

I.

Olson,

Acta

Chem.

Scund.,

1965,

19,

1915.

212

R.

G.

Denning,

J.

Chem. Phys.,

1966,

45,

1307.

213

E.

Larsen and

S.

F.

Mason,

J.

Chem.

SOC.

(A),

1966, 313;

K.

Garbett and

R.

D.

Gillard,

ibid.,

p.

802;

J.

H.

Dunlop,

R.

D.

Gillard, and

R.

Ugo,

ibid.,

p.

1540;

J.

I.

Legg

and

D.

TV.

Cooke,

Inorg.

Chem.,

1966,

5,

594;

M.

D.

Alexander and

D.

H.

Busch,

ibid.,

p.

602;

R.

G. Denning and

T.

S.

Piper,

ibid.,

p.

1056;

B.

E.

Bryant,

H.

J.

Hu, and

W.

H.

Glaze,

ibid.,

p.

1373;

N. Matsuoka,

J.

Hidaka, and

Y.

Shimura,

Bull.

Chem.

SOC.

Japan

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

202

INORGANIC

CHEMISTRY

The preparation, and assignment of structures from spectroscopic

measurements, of complexes

of

the types [Co(tetram)XY]+ (tetram

is

a

cyclic quadridentate-amine

;

X

and Y can be halide

or

pseudo-halide groups),

[Co en2&YIn+

(X

=

a

primary aliphatic amine;

Y

=

C1,

Br

or

X

=

glycin-

ato,

Y

=

Cl), [Co(dmg),XL] (dmg

=

dimethylglyoximato;

X

=

thiourea;

L

=

mono-deprotonated thiourea), and trans-[Rh en,X2]N03 (X

=

C1, Br)

have been rep0rted.2~~ The peroxy-bridged complexes

trans-[X(

cyc1am)Co-

O,Co(cyclam)

XI2+

(cyclam

=

1,4,8,11-tetra-azacyclotetradecane;

X

=

C1,

N3,

NCS,

NO,)

have been isolated and converted into trans-[Co(cyclam)XY]+

by reaction with acids HY.216

An

X-ray structural study of the complex

[(NH3),Co02Co(NH,)],(S0,)HS0,),

has been interpreted

in terms of

a

bridging superoxide

(02-)

rather than a peroxide group.216

[RhH(H20)(NH,)4]S0,,217 K2[RhH(CN)4H20],21g [IrHxY3-,L,]

(x

=

1,2,

or

3;

Y

=

halogen; L

=

R3P, R,As), [IrH,(PR,),],219 and [IrH,(PMe,Ph),]

(Y

=

C1,

Br, I, H, CN, SCN),220 have been given, and infrared and n.m.r.

spectra used to determine stereochemistries. The infrared spectra

of

some

bis-ethylenediamine-cobalt

(III),

halogeno-iridium(m) arsine

or

phosphine

complexes, [RhCl,,SRCN], [RhCl,(TPP)], and [MX,(TPP),]

(M

=

Pd,

Pt,

Hg;

X,

C1,

Br;

TPP

=

1,2,54riphenylphosphole)

have also been discussed

in relation to the possible structures of the complexes.22l

Nickel,

Palladium,

and

Plathum.-The compounds of stoicheiometry

Pt(PPh,) and Pt(PPh,), have been prepared, and the mono-derivative is

shown to be tetrameric in benzene solution.222

A

new and convenient

preparation

of

Ni(PF3)4 from nickelocene and

PF,

has been reported.223

The reaction of Pt(PPh,), with hydrochloric acid has been shown to give

a

series

of

hydride complexes, whereas the corresponding palladium and nickel

complexes, and [M(Ph,P(CH2)2PPh2),]

(M

=

Ni, Pd, Pt), gave only hydro-

gen.224 The reaction between Pt(PPh,), and

CS,

or COS resulted in the

isolation

of

monomeric compounds, [(Ph,P),Pt L]

(L

=

CS,, COS).225

The preparations of some hydrido-complexes, [RhH(NH,),]SO,,

1966,

39,

1257;

K.

Ohkawa,

J.

Hidaka, and

Y.

Shimura,

ibid.,

p.

1715;

M. Shibatu,

H.

Nishikawa, and

Y.

Nishida,

ibid.,

p.

2310;

T.

P. Emmenegger and

G.

Schwarzenbach,

Helv.

Chim.

Acta,

1966,

49,

625;

F.

P.

Dwyer,

I.

K.

Reid, and

A.

M. Sargeson,

Austral.

J.

Chem.,

1965,

18,

1919;

J.

A.

Broomhead,

Nature,

1966,

211,

741.

214

S.

C.

Chan and

F.

Leh,

J.

Chern.

SOC.

(A),

1966, 760;

P.

0.

Whimp and

N.

F.

Curtis,

ibid.,

p.

867;

J.

P.

Collman and

P.

W. Schneider,

Inorg.

Chem.,

1966,

5,

1380;

M.

D.

Alexander and

D.

H.

Busch,

ibid.,

p.

1590;

A. V.

Ablov,

B.

A.

Bovykin,

and

N.

M.

Samus,

Russ.

J.

Inorg.

Chem.,

1966,

11,

31;

R.

D.

Gillard,

E.

D

McKenzie, and

M.

D.

Ross,

J.

Inorg. Nuclear

Chern.,

1966,

28,

1429.

215

B.

Bosnich,

C.

K.

Poon, and

M.

L.

Tobe,

Inorg.

Chem.,

1966,

5,

1514.

216

W.

P.

Schafer and

R.

E.

Marsh,

J.

Arner.

Chem.

SOC.,

1966,

88,

178.

217

J. A. Osborn,

A.

R.

Powell, and

G.

Wilkinson,

Chem.

Comm.,

1966, 461.

218

D.

N.

Lawson,

M.

J. Mays, and

C.

Wilkinson,

J.

Chem.

SOC.

(A),

1966, 52.

21g

J. Chatt,

R.

S.

Coffey, and B.

L.

Shaw,

J.

Chem.

Soc.,

1965, 7391.

220

J.

M.

Jenkins and

B.

L.

Shaw,

J.

Chm.

SOC.

(A),

1966, 1407.

821

R.

A.

Walton,

J.

Chem.

SOC.

(A),

1966, 365;

J.

M. Jenkins and

B.

L.

Shaw,

J.

Client. SOC.,

1965,6789;

M.

N.

Hughes and W.

R.

McWhinnie,

J.

Inorg.

Nuclear

Chem.,

1966,

28,

1659;

B.

F.

G.

Johnson and

R.

A. Walton,

ibid.,

p.

1901,

Zz2

R.

Ugo,

F.

Cariati, and

G.

LaMonica,

Chem.

Comm.,

1966, 868;

R.

D.

Gillard,

R.

Ugo,

F.

Cariati,

S.

Genini, and

F.

Bonati,

ibid.,

p.

869.

223

J.

F.

Nixon,

Chem.

Comrn.,

1966, 34.

224

F.

Cariati,

R.

Ugo,

and

F.

Bonati,

Inorg.

Chem.,

1966,

5,

1128.

226

M.

C.

Baird and

G.

Wilkinson,

Chem.

Comm.,

1960, 614.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

MABBS

AND

MACHIN:

THE

TRANSITION

ELEMENTS

203

Diamagnetic, square-planar dithiolate complexes [M(dt)2]2-

[M

=

Ni,

Pd,

Pt,

Cu; dt

=

S2CS2-, S2CNCN2-, S2CC(CN)22-] have been isolated.Z26

It

bas

been proposed that the occurrence of isotropic g-values close to the

free-electron value,

in

complexes of the type [Ni(mnt),]-, is diagnostic

evidence for the presence

of

cation-stabilised free radicals.

227

The existence

of an electrontransfer series of general formula

[MLJ

(M

=

Ni,

Co,

Cu,

Zn, Cd;

L

=

catechol, tetrachlorocatechol) has been demonstrated using

electrochemical oxidation, e.s.r., and chemical methods.22* The complexes

C]SI(S,C,Ph,),]

(M

=

Ni, Pd) react with Ph,P(CH,),PPh,(diphos) to give

compounds

[M(

S2C,Ph2) (diphos)], whereas the corresponding platinum com-

pound only gives an adduct,

[Pt

(S,C,Ph,),(diphos)].

229

The low-temperature single-crystal polarised spectrum

of

K2PtC14230 and

the circular dichroism

of

the

[PtC1,I2-

ion

231

have been discussed in relation

to

their structures.

A

discussion of the effect

of

a

distant asymmetric centre

on the circular dichroism

of

the complexes truns-[PdCl,( -)amz] and

trans-

[PdCl,( -)amz] (am

=

l-phenylethylamine) has also been given.232

The effect

of

spin-orbit coupling, an axial ligand-field component, and

an orbital reduction factor,

k,

on the magnetic properties

of

the

3T1

term

has been calculated, and the results are used to interpret the observed

magnetic behaviour of

a

series of tetrahedral Ni(n) cornple~es.23~

The

diamagnetism

of

[Ni(diarsine),](

ClO,),

has been interpreted on the basis of

an octahedral arrangement

of

ligands, which has electrical symmetry of

D,,

arising from

0-

and n-b~nding.~~~

The crystal-field terms which arise for

nickel(@

in

trigonal- bipyramidal and square-pyramidal stereochemistries

have been calculated, and the predicted spectral transitions found to be in

satisfactory agreement with those 0bserved.~~5 The effects of clustering,

and of exchange interactions between nickel@) ions

in

some Perovskite

fluoride complexes, on the electronic absorption spectra are reported.236

The proton magnetic resonance contact shifts in a number of nickel@)

Schiff base, nitrogen and oxygen donor, and diphosphine complexes have

been used to suggest possible modes of electron-spin delocalisation and the

existence equilibria between complexes with different stereochemistries.

237

2z6

J.

P.

Fackler, jun., and

D.

Coucouvanis,

J.

Amer. Chem.

SOC.,

1966,

88,

3913;

227

A.

H.

Maki,

T.

E.

Berry,

A.

Davidson,

R.

H.

Holm, and

A.

L.

Balch,

J.

Amer.

228

F.

Rohrscheid,

A.

L.

Balch, and

R.

H.

Holm,

Inorg. Chem.,

1966,

5,

1542.

22g

V.

P.

Mayweg and

G.

N.

Schrawzer,

Chem. Comm.,

1966, 640.

230

D.

S.

Martin, jun.,

M.

A.

Tucker, and

A.

J.

Kassman,

Inorg.

Chem.,

1965,

4,

231

B.

Bosnich,

J.

Amer. Chem.

SOC.,

1966,

88,

2606;

D.

S.

Martin,

J.

G.

FOSS,

M.

E.

232

B.

Bosnich,

J.

Chem.

Xoc.

(A),

1966, 1394.

233

B.

N.

Figgis,

J.

Lewis,

F.

E.

Mabbs,

and

G.

A.

Webb,

J.

Chem.

SOC.

(A),

1966,

a34

B. Bosnich,

R.

Bramley,

R.

S.

Nyholm,

and M.

L.

Tobe,

J.

Amer.

Chem.

SOC.,

235

M.

Ciampolini,

Inorg. Chem.,

1966,

5,

35.

236

W.

W. Holloway, jun., and

M.

Kestigian,

J.

Chem. Phys.,

1966,

45,

639;

J.

Ferguson and

H.

J.

Guggenheim,

ibid.,

p.

1095.

237

R.

W. Kluiber and

W.

Dew.

HOITOC~,

jun.,

Iwg.

Chem.,

1966,

5,

152;

J.

D.

Thwaites and

L.

Sacconi,

ibid.,

p.

1029;

J.

D. Thwaites,

J.

Bertini,

and

L.

Sacconi,

ibid.,

p.

1036;

G.

R. van

Hecke

and W. Dew. Horroclm, jun.,

ibid.,

p.

1968;

R.

Holm

R.

G.

Werden,

E.

Billig, and

H.

B.

Gray,

Inorg. Chem.,

1966,

5,

78.

Chem.

SOC.,

1966,

88,

1080.

1682; 1966,

5,

1298.

McCarville,

M.

A.

Tucker, and

A.

J.

Kassman,

Inorg. Chem.,

1966,

5,

491.

1411.

1966,

88,

3926.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

204

INORGANIC CHEMISTRY

As

with cobalt(@, infrared, electronic spectra, magnetic susceptibility,

molecular weight, and conductivity data have been used to suggest structures

for

the following types

of

complexes: [ML,X,]

(M

=

Ni, Pd, Pt;

L

can be

mono thio

-

p-

diket one, quinoline

,

i

so

quinoline

,

di methylp yridines

,

2 -methyl-

benzimidazole, 3 -methylis0 quinoline, 2

-

methylbenzothiazole,

2

-,

3

-

or

4-cyanopyridine

;

X

can be

C1,

Br,

I,

NCS,

dicyanamide, tricyanmethanide,

substituted pyridines, bipyridyl, substituted

1

,lo-phenanthrolines)

;23*

[NiL,] (L

=

1,5-diazacyclo-octane, Schiff bases derived from diketones and

aromatic amines

or

from salicylaldehydes and substituted trimethylene-

diamines)

;

239

[INiLYX]

,nH,O

{L

=

2,12-dimethyl-3,7

,

1

1,17- tetra-azabicyclo-

[11,3,1]heptadeca-1(17),2,11,13,15-pentaene;

Y

=

X

=

ClO,,

n

=

0;

Y

=

X

=

C1,n

=

0;Y

=

X

=

NCS,n

=

0;Y

=

X

=

Br,n

=

l;Y

=

Br,

X

=

BF,,

n

=

1);24*

[M,X,L]

[M

=

Pd(rr), Pt(rr);

X

=

Cl,

Br,

I,

SCN;

L

=

1,4-di-

(o-aminothiophenoxy)but-trans-2-ene].

The occurrence of

diketones bonded through a carbon atom rather than the oxygena has been

reported in complexes

of

the type [Pt(diketone),X]-

(X

=

C1,

Br).

These

complexes can then co-ordinate, through the diketone oxygen atoms, to

other transition metals to give compounds

of

the type M[Pt(acac),X],

(M

=

Mn,

Fe,

Co,

Ni,

Cu,

Zn, Cd, Pd).,,, The isolation

of

compounds

K3Ni(CN),,2H,0 and Mvi(CN),],2H20

{M

=

[Cr(NH,),I3+, [Cr en3I3+},

which contain the [Ni(CN),]3- ion, and the stability

of

this ion towards

decomposition to [Ni(CN),]2- has been reported.

243

A

number

of

palladium(n), platinum(II), cadmium(n), and mercury(n)

halide and silver(1) perchlorate complexes with the ligands Ph3PSe and

Ph,AsS have been prepared and their infrared spectra discussed with respect

to

P-Se and

As-S

stretching vibrations. Platinum-silicon and platinum-

germanium bonds have been reported

to

occur in the complexes

[Me3M-Pt(C1)(PEf3),]

(M

=

Si, Ge),245 whilst the Pr,Sn, cluster is thought

to be present in the ion [Pt3Sn,C1,,]4-.246

A

cyclic structure, in which

approximately square-planar NiS, units

form

the faces

of

it

hexagonal prism,

has been proposed for [Ni(

SR),],

comp0unds.~4~ Infrared absorption bands

G.

W. Everett, jun., and W. Dew.

Horrocks,

jun.,

J.

Anzer.

Chem,.

SOC.,

1966,

88,

1071;

B. B.

Wayland,

R.

S.

Drago, and

H.

F.

Henneike,

ibid.,

p.

2455;

L.

Morpurgo and

R.

J.

P.

Williams,

J.

Chem.

SOC.

(A),

1966, 73.

238M.

Goodgame and

M.

J.

Weeks, J.

Chem.

Soc.

(A),

1966, 1156;

P.

L.

Goggin

and

R.

J.

Goodfellow,

ibid.,

p.

1462;

R.

A.

Walton,

J.

Inorg. Nuclear

Chem.,

1966,

28,

2229;

L. Sacconi and

I.

Bertini,

Inorg.

Nuclear Chem. Letters,

1966,

2,

29;

S.

H.

H.

Chaston,

S.

E.

Livingstone, and

T.

N. Lockyer,

Austral.

J.

Chem.,

1966,

19,

1401;

H.

Kohler,

H.

Hartung, and B. Seifert,

2.

Anorg.

Chem.,

1966,

34'7,

30.

239

W.

K.

Musker and

M.

S.

Hussain,

Inorg.

Chem.,

1966,

5,

1416;

L.

Sacconi,

N.

Nardi, and

F.

Zanobini,

ibid.,

p.

1872;

S.

Yamada,

H.

Xshikawa, and

E.

Yoshida,

Bull.

Chern.

SOC.

Japan,

1966,

39,

994.

240

J.

L.

Karn and D.

H.

Busch,

Nature,

1966,

211,

160.

z41D.

C.

Goodall,

J.

Chem.

Soc.

(A),

1966, 1562.

242

J.

Lewis,

R.

F.

Long, and

C.

Oldham,

J.

Chem.

SOC.

(A),

1965, 6740;

D. Gibson,

J.

Lewis, and

C.

Oldham,

J.

Chem.

SOC.

(A),

1966, 1453.

243

W.

C.

Andersen and

R.

H.

Harris,

Inorg.

Nuclear Chem. Letters,

1966,

2,

315;

K.

N.

Raymond and

F.

Basolo,

Inorg.

Chem.,

1966,

5,

949.

244

P.

Nicpon and

D.

W.

Meek,

Chem. Comm.,

1966, 398.

245

F.

Glockling and

K.

A.

Hooton,

Chem.

Comm.,

1966, 218.

R.

V.

Lindsey, jun.,

G.

W.

Parshall, and

V.

G. Stolberg,

Inorg.

Chern.,

1966,5, 109.

E.

W.

Abel

and

B.

C. Crosse,

J.

Chem.

Soc.

(A),

1966, 1377.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

MABBS

AND MACHIN:

THE

TRANSITION ELEMENTS

205

have been assigned to the various vibrational modes in nickel@), palla-

dium(=), and copper(

n)

bis- (oxamido)-complexes,24~ to metal-nitrogen

stretching vibrations

in

palladium(

11)

,

platinum(=) and rhodium(

m)

halide

MeCN, PhCN, and bipyridyl cornple~es,~4~ and to stretching vibrations

of

the azide group

in

the compounds [Ph4As]2[Pt(N3)4]H20, [Ph,As],[Pt(N,),],

and [Ph,As][Au(N,),]. The magnetic data, electronic and infrared spectra

of Rb,~i(NO,),] were reported to be consistent with

a

distorted octahedral

structure involving nitrogen co-ordinated and either chelating or symmetri-

cally bridging nitrite groups.

251

Similar spectra measurements indicate the

presence

of

nitro groups in the complexes [NiL,(NO,),]

(L

=

a

substituted

ethylenediamine), although in chloroform solution some

of

the complexes

showed an equilibrium between nitro and nitrito groups.252

The complex (NO,+)[Ni(NO,),], which has

peE

=

4-54

B.M.

at

21"c,

was reported to be the first known example

of

a high-spin Ni(m) c0mplex.~5~

The reaction between palladium and nitric acid has been shown to give

[Pd(NO,),(OH),], which can then react with

N204

to

give [Pd(N03),2N204],

or

with

N,O,

to give the simple nitrate, Pd(N0,),.254

The reaction between

bromine trifluoride and the compounds M,[PtCl,]

(M

=

K,Rb,Cs,NO+)

gave M',[PtC13F3], except in the case

of

M

=

NO+,

when (NO),[PtF,] was

formed.255

The infrared and Raman spectra

of

K,[Pt(CN),Cl,] were re-

ported, and the force constants for bond stretching calc~lated.~5~ The

preparations and magnetic properties

of

the compounds

M[PtF,]

(M

=

XeF,,

NO,

NO,)

have been described.257 The reaction between

PtF,

and ClF,

gave

a

compound which infrared data suggest should be formulated as

[ClF,]

+[PtF,]-.

With

PtF,

and tetrafluorohydrazine,

PtF,

and

PtF4

were

produced succe~sively.25~

Copper, Silver,

and

Gold.-The infrared and Raman spectra

of

compounds

containing the ions [Cu(CN),]-, [CU(CN),]~-, and [Cu(CN)JS- have been

discussed in terms of possible stereochemistries and modes

of

bonding

in

these ions.259 Infrared spectral studies on pressed discs of

KBr

and

KAu(CN), showed that solid solutions were not formed, but that [Au(CN),]-

groups remained in clusters.260 The preparations

of

complexes of the type

[ML,]X

(L

=

8-methylthioquinoline, 8-benzylthioquinoline

;

M

=

Cu,

Ag

;

248

P.

X.

Armendarez and

K.

Nakamoto,

Inorg. Chem.,

1966,5, 796.

249

R.

A.

Walton,

Canad.

J.

Chem.,

1966,

44,

1480.

250

W.

Beck,

E.

Schuierer,

and

K.

Feldl,

Angew. Chem., Internat.

Edn.,

1966,

5,

251

B.

J.

Hathaway and

R.

C.

Slade,

J.

Chem.

SOC.

(A),

1966, 1485.

252

D.

M.

L.

Goodgame and

M.

A. Hitchman,

Inorg. Chem.,

1966,

5,

1303.

253

C.

C.

Addison and

B.

G. Ward,

Cl2em.

Cornrn.,

1966, 819.

254 C.

C.

addison and

B.

G.

Ward,

Chem.

Cmm.,

1966,

155.

255

D.

H.

Brown,

K.

R.

Dixon,

and

D.

W.

A.

Sharp,

J.

Chem.

SOC.

(A),

1966,

256

L.

H.

Jones and

J.

M.

Smith,

Inorg. Chem.,

1965,

4,

1677.

257

T.

I?.

Gortsema and

R.

H.

Toeniskoetter,

Inorg. Chern.,

1966,5, 1217;

N. Bartlett

and

S.

P.

Beaton,

Chem.

Cotnm.,

1966, 167;

N.

Bartlett,

F.

Einstein,

D.

F.

Stewart,

and

J.

Trotter,

ibid.,

p.

550.

258

F.

P.

Gortsema and

R.

H.

Toeniskoetter,

Inorg. Chem.,

1966,

5,

1925.

259

D.

Cooper and

R.

A. Plane,

Inorg. Chem.,

1966,

5,

16;

J.

D.

Graybeal and

G.

L.

McKown,

ibid.,

p.

1909;

M.

J.

Reisfeld, and

L.

H.

Jones,

J.

~Wol.

Spectroscopy,

1965,

260

L.

H.

Jones

and

I

K.

Kressin,

J.

Chem.

Phys.,

1965,

43,

3956.

249.

1844.

18,

222.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

206

INORGANIC

CHERTISTRY

X

=

ClO,)

have been described.261 The characterisation and suggestions

for the structure of the ion [Au,(DPE),cl]+ (DPE

=

1,2-bisdiphenylphos-

phinoethane) have been reported.

262

The reaction between

[

(Ph,P),CuBH,]

and perchloric

or

tetrafluoroboric acids resulted in compounds containing the

[(Ph3P)2Cu(BH,)Cu(PPh3)2]+

ion, for which

it

structure with four bridging

hydrogens between the copper and boron atoms

was

pr0posed.~6~ The

presence of carbon bonded acetylacetone has been demonstrated in the

compounds

[(

R,P)A~(acac)].~~~ The rapid evolution of carbon dioxide from

solutions of CuCl and CCl, in

Me2S0

has been interpreted in terms of the

following reactions

:265

8CuCl

+

CCI,

+

Me,SO

=

[4cu(I)

+

~CU(II)

+

12C1-]

+

CO

+

Me,S

The preparations of [(Et,P)Au

Y]

[Y

=

alkyl or aryl mercaptides,

SCN,

SC

(S)NEt,

,

SC(

S)

OEt

,

SC(

NH,)&E€,

+Br

-1,

[

(PhO),PAuCl]

,

[

(

R3P) ,Au]

+

(R

=

Et

or

Ph), and [R,Au

XI

(R

=

Bu, Ph; X

=

C1, Br,

SCN)

have been

described.266

The magnetic susceptibilities

of

the following compounds have been inter-

preted in terms of their probable structures and the occurrence of magnetic

exchange interactions (in some cases estimates

of

the magnitudes

of

these

interactionsihave been made)

:

{Cu(02C[CH,],C02)} ;267 [(R,N)CU(CH,CO,)~X]

(X

=

NCS, NO,, Br);268 [Cu(RR'CHCO,),]

(R

=

R'

=

Et;

R

=

H

and

(butanol)]

(X

=

H,

p-Me, p-MeO, p-Br,

p-N02);270

[CuL2X2] and [CuLX,]

(L

=

substituted pyridine N-oxide; X

=

halide),271 [Cu(AO)X]

A0

=

amino-alcoholates;

X

=

halide)

;2'2

bis-(imidazolato)Cu(~~),~~~

and X-sal-c-

aminophenol)Cu(11).274 In the copper acetate dimer support for the &bond-

ing model for the metal-metal interaction has been obtained from 63Cu

nuclear magnetic resonance.

275

Molecular orbital calculations on some bis- (p-diketone)Cu(n) complexes

have been reported, and the results compared with e.s.r. and electronic

spectral measurements.276 Similarly, molecular orbital calculations have

261

F.

Hein and K.-H. Vogt,

Annalen,

1965,

689,

202;

F.

Hein

and K.-H. Vogt,

2.

anorg.

Chem.,

1965,

340,

46.

262

L.

Naldini,

F.

Cariati, G. Simonetta, and L. Malatesta,

Chem. Comm.,

1966, 647.

263

F.

Cariati and L. Naldini,

J. Inorg.

Nuclear Chem.,

1966,

28,

2243.

264

D.

Gibson,

B.

F.

G.

Johnson,

J.

Lewis, and

C.

Oldham,

Chem.

and Ind.,

1966,342.

265

R.

R.

Lavine,

R.

T.

Iwamoto, and

J.

Kleinberg,

J.

Amer.

Chem.

SOC.,

1966,

88,

366

(x.

E.

Coates,

C.

Kowala, and

J.

M.

Swan,

AustmE.

J.

Chem.,

1966,

19,

539.

267

L.

Dubricki,

C.

M.

Harris,

E.

Kokot, and

R.

L.

Martin,

Inorg.

Chem.,

1966,

5,

268

D.

M.

L.

Goodgame and D.

F.

Marsham,

J.

Chem.

SOC.

(A),

1966, 1167.

26D

W.

E.

Hatfield,

H.

M.

McGuire,

J.

S.

Paschal, and

R.

Whyman,

J.

Chcm.

SOC.

(A),

270

W.

E.

Hatfield,

C.

S.

Fountain, and

R.

Whyman,

Inorg.

Chem.,

1966,

5,

1855.

271

W.

E.

Hatfield and

J.

C.

Morrison,

Inorg.

Chem.,

1966,

5,

1390;

Y.

Muto and

273

E.

Uhlig and

K.

Staiger,

2.

anorg.

Chem.,

1966,

346,

21.

273

M.

Inoue,

M.

Kiahita, and M. Kubo,

Bull.

Chem.

SOC.

Japan,

1066,

39,

1352.

274

W.

E.

Hatfield and

F.

L.

Bunger,

Inorg.

Chem.,

1966,

5,

1161.

276

H.

C. Allen, jun.,

J.

Chem. Phys.,

1966,

45,

553;

F.

A.

Cotton and

J.

J.

Wise,

CO

+

Me,SO

=

CO,

+

Me,S

R'

=

CN, MeO,

EtO,

PhO,

CT-ClC6H40,

p-NO,C,H,O)

;269

[CU(X-CGH,CO2)2-

4304.

93;

B.

N.

Figgis and D.

J.

Martin,

ibid.,

p.

100.

1966, 1194.

H.

B.

Jonassen,

Bull.

Chem.

SOC.

Japan,

1966,

39,

58.

D.

J.

Rogers,

Inorg.

Chem.,

1965,

4,

1830.

J.

Amer. Chem.

SOC.,

1966,88, 3451;

G.

N.

LaMar,

Acta

Chem.

Scad.,

1966,20, 1359.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

MABBS

AND

MACHIN:

THE

TRANSITION

ELEMENTS

207

also been made

for

[cu(m3)6]2+9 [c~(H,o),]~+, and copper(II) in tetrahedral,

square-planar, and octahedral chloride environments.

277

The interpretation

of

the optical and e.s.r. spectra

of

[CuC1,I2-, dissolved in Cs,ZnCl, and

(Me4N),ZnC1, host lattices, has led to the proposal that the

low

symmetry

of the ion is an intrinsic property, for which the dominant mechanism is the

Jahn-Teller effect.

278

Quinqueco-ordinated copper(n) was reported to occur in the complexes

[X-salen-N(R)R'],Cu

(R

=

H orMe and R'

=

Me), [Cu(mepic),X](ClO,)

(mepic

=

6-methyl-2-picolylamine;

X

=

halide),

[(A)Cu-(CN)-Cu(A)](C1O4),

(A

=

hexamethyltetra-azacyclotetradecadiene),27s

and [Cu(bipy),X] (X

=

halide). This last compound is thought to have a compressed trigonal-

bipyramidal structure. Based on spectral and magnetic evidence, tetra-

gonally distorted octahedral structures have been assigned to the complexes

[Cu(NH,),]X, (X

=

C1-,

Br-,

I-,

BF4-, ClO,-) and [Cu(ben~imidazole)~X,]

(X

=

C1,

Br,

NO,,

ClO,,

NCS,

+SO,).2s1

The Raman spectra of powdered samples and solutions

of

compounds

containing the ions [MX,]"-

(M

=

Au;

X

=

C1, Br,

I;

n

=

1

:

M

=

Pt:

X

=

C1, Br,

I;

n

=

2:

M

=

Pd; X

=

C1,

Br;

n

=

2)

have been examined

and

M-X stretching force constants estimated.

282

The compound

Cs,K[AgF,]

has

been prepared and its magnetic moment reported

to

be

2.6

BM.,83

Zinc,

Cadmium,

and

Mercury.-The bond stretching force constants

El(Hg-Hg), E,(Hg-X) and the interaction constant,

El,,

between adjacent

bonds in the compounds Hg,X, (where

X

=

C1, Br H,O) have been estimated

from their Raman spectra.

284

The isolation

of

compounds Hg2L4(C10,),

[L

=

Ph,PO,

pyN0, (CH,CH,CH,),SOJ, Hg,L,SiF, (L

=

Ph,PO,pyNO),

Hg,(Me,SO)SiE",,xH,O, Hg2(Me,SO),.,(C10,), and HgNO, has been re-

ported.2s5 Metal-phosphorus vibrations in the complexes [(Ph,P),MX,]

(M

=

Zn, Cd, Hg; X

=

C1,

Br,

I)

have been assigned to bands in the

98-166

cm.-l region.286 Frequency assignments have also been made from

the Raman spectra

of

[M

en,]X,

(M

=

Zn, Cd, Hg; X

=

and

of

aqueous solutions of Hg(CN), and halide ions.,g8

The preparations

of

1

:

1

addition compounds between

1

,3,5-trithian9

HgX, (X

=

C1, Br,

I),

and AgX (X

=

NO,,

C1, Br,

I)2s9

and of the com-

plexes [ZnB,X,], [ZnB,X,], [ZnB,X,]

(B

=

py, 4-Me py, %Me py;

X

=

C1,

277

P.

Ros

and

G.

C.

A.

Schuit,

Theor. Chim. Acta,

1966,

4,

1;

B.

ROOS,

Ada

Chem.

Scand.,

1966,

20,

1673.

278

M.

Sharnoff and

C.

W. Reimann,

J.

Chem.

Phys.,

1965,

43,

2993.

279

Y.

M.

Curtis and

N.

T.

Curtis,

Awtral.

J.

Chem.,

1966,

19,

609;

L.

Sacconi and

I.

Bertini,

Inorg.

Chem.,

1966, 5,1520;

S.

Utsuno and

K.

Sone,

J.

Imrg.

Nuclear Chem.,

1966,

28,

2647.

2so

H.

Elliott,

B.

J.

Rathamay, and

R.

C.

Slade,

J.

Chem.

SOC.

(A),

1966,

1443.

281

M.

Goodgame and

L.

J.

B.

Haines,

J.

Chem.

SOC.

(A),

1966, 174;

H.

Elliott and

B.

J.

Hathaway,

Inorg.

Chem.,

1966,

5,

885.

282

P.

J.

Hendra,

Nutwe,

1966,

212,

179.

283

R.

Hoppe

and

R.

Homann,

Naturwiss.,

1966,

53,

501.

286

R.

A.

Potts and A.

L.

Allred,

Inorg.

Chem.,

1966,

5,

1066.

286

G.

B. Deacon and

J.

H.

S.

Green,

Chem.

Comm.,

1966, 629.

287

K.

Krishnan and

R.

A. Pla.ne,

Inorg.

Chem.,

1966,

5,

852.

28*

R.

P.

J.

Cooney and

J.

R.

Hall,

J.

Inorg. Nuclear

Chem.,

1966,

28,

1679.

J.

A.

W.

Dalziel

and

T.

G. Hewitt,

J.

Chem.

SOC.

(A),

1666,

233.

H.

M.

Gager,

J.

Lewis,

and

M.

J.

Ware,

Chem. Comm.,

1966, 616.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

208

INORGAN%C

CHENISTRY

Br,

I,

NCS)290

have been described.

From

infrared spectra and the iso-

morphous inclusion

of

cobalt(I1) ions, it was concluded that [ZnB,X2],

[ZnB,X,],

and [ZnB,X,] have tetrahedral, five-co-ordinate, and octahedral

structures, respectively. Mercury-silicon and zinc-germanium bonding is

reported in

[

(Ph,Si),Hg]

291

and [Zn(GePh,),],

292

respectively.

290

D.

P.

Graddon,

K.

B.

Henig, and

E.

C.

Watton,

Aust~al.

J.

Chem.,

1966,

19,

1801.

2Q1

R.

A.

Jackson,

Chena.

Cmm.,

1966,

827.

2n2

E.

Amberger,

W.

Stoeger,

and

R.

Honigschmid-Grossich,

Angew.

Chem.,

Internat.

Edn.,

1966,

5,

522.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

5.

TRANSITION-METAL CARBONYLS AND

RELATED COMPOUNDS

By

F.

J.

Kohl

and

J.

Lewis

(Department

of

Chemistry, University

of

Manchester)

THE

techniques for the preparation

of

metal carbonyls and olefin derivatives

have been summarised,l the reactions of ligands co-ordinated with transition

metals have been reviewed,2 the application

of

n.m.r. in organometallic

chemistry has been summarised,x and the chemistry

of

the Group

VIB

carbonyls

4

and the nqture

of

sulphur- and phosphorus-bridged complexes

of

the transition metals have been ~urveyed.~ Reviews have appeared on

the cyclopentadiene and arene metal carbonyls,6 hydride complexes,'

nitrosyl-metal complexes,g metal cl~sters,~ the electronic structures

of

organometallic molecules,1* and acylation reactions,

l1

as well as fluorine

organometallic complexes,l2,

13

metal-ally1 complexes,

l*

and cyclic-organic

metal derivatives.l5

An

extensive survey

of

the chemistry

of

nickel-cyclo-

octadiene systems has been given.16

An

English edition

of

"

Metal n-Complexes

"

by Fischer and Werner has

been published;l7

books

on metal hydrides

l8

and benzoid-metal complexes

have also appeared. Seyferth and

King

have produced an annual survey of

organometallic chemistry, and this must be considered as one

of

the more

outstanding texts

of

the year;20 it provides a valuable service to the field.

Structure.-A

theoretical assessment

of

the bonding in metal car-

bonyls

21

and unsaturated hydrocarbon derivatives

of

iron and chromium

22

H.

F.

Holtzclaw,

jm.,

Inorg. Synth.,

1966,

7,

178.

J. P. Collman,

Transition Metal Chem.,

1966,

2,

2.

S.

L.

Stafford and

H.

D.

Kaesz,

Adv. Organometallic Chem.,

1965,

3,

1.

G.

R.

Dobson,

I.

W.

Stole, and

R.

K.

Sheline,

Adv. Inorganic Chemzstry Radio-

chem.,

1966,

8,

1.

ti

R.

G.

Hayter,

Preparative Inorg. Reactions,

1965,

2,

211.

*

R.

L.

Pruett,

Preparative Inorg. Reactions,

1965,

2,

187.

A.

P.

Ginsberg,

Transition Metal

Chem.,

1965,

1,

112.

*

B.

F.

G.

Johnson and J.

A.

McCleverty,

Progr. Inorg. Chem.,

1966,

7,

277.

O

F.

A.

Cotton,

Quart. Rev.,

1966,

20,

389.

lo

D.

A.

Brown,

Transition Metal Chem.,

1966,

2,

2.

l1

F.

Calderazzo and K. Noack,

Coordination Chem. Rev.,

1966, 118;

R.

F.

Heck,

l2

R.

D.

Chambers and

T.

Chivers,

Organometallic Chem. Rev.,

1966,

1,

279.

l3

F.

G.

A.

Stone,

Endeavour,

1966,

25,

33.

l4

G.

Wilke,

B.

Bogdanovid,

P.

Hardt,

P.

Heimbach,

W.

Keim,

M. Kroner, W.

Oberkirch,

K.

Tanaka,

E.

Steinbriicke,

D.

Walter, and

H.

Zimmermann,

Angew. Chem.,

1966,

78,

157.

l5

P.

M.

Maitlis,

Adv. Organometallic Chem.,

1966,4,95;

M.

A.

Bennett,

ibid.,

p.

353;

H.

Cais,

Organometallic Chem. Rev.,

1966,

1,

433.

l6

B. Bogdanovic,

M.

Kroner, and

G.

Wilke,

Annalen,

1966,

699,

1.

l7

E.

0.

Fischer and

H.

Werner,

"

Metal .rr-Complexes," Elsevier, Amsterdam,

1966.

l8

K.

M.

Mackay,

"

Hydrogen Compounds

of

the Metallic Elements," Spon, London,

lo

H.

Zeiss,

P.

J. Wheatley, and

H.

J.

S.

Winkler,

"

Benzoid-Metal Complexes,"

2o

D.

Seyferth and

R.

B.

King,

Ann.

Survey Organometallic Chem.,

1965,

1.

21

S.

F.

A.

Kettle,

J.

Chem.

SOC.

(A),

1966, 1013, 420.

22

B. J. Nicholson,

J.

Amer. Chem.

Soc.,

1966,

88,

5156.

Adv.

Organometallic Chem.,

1966,

4,

243.

1966.

Ronald Press, New York.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

210

INORGANIC

CHEMISTRY

tri-carbonyl has been discussed. The carbonyl stretching frequencies

in

the

infrared spectra

of

complexes have been considered theoretically, and changes

in

bonding forces shown to be associated with n-electron effects.23 The

intensity

of

both carbonyl and nitrosyl vibrations has been correlated

to

the bond angle between the groups and the theory applied to an extensive

series

of

comp0unds.~4 The relative intensities

of

the two

%

vibrations of

compounds of the form

XMh(CO),

have been considered

in

terms of coupling

and distortionof bond angles at themetal away from The low-frequency

spectra

(700-200

cm.-l)

of

a series of manganese carbonyl derivatives

Mn(CO),L

(L

=

halogen

or

alkyl) have been measured and discussed with

relation to the carbonyl stretching modes.

26

Mass spectroscopic measure-

ments are now being extensively applied to organometallic and carbonyl

systems. The negative-ion mass spectra of nickel, iron, chromium, molyb-

denum, and tungsten carbonyl have been determined.2' The utilisation

of

mass spectra in the determination of the number of hydrogen atoms in the

carbonyl hydrides of manganese, rhenium, and ruthenium has been empha-

sised,28 whilst the spectra of some polynuclear carbonyls and related com-

pounds of manganese, molybdenum, rhenium, iron, ruthenium, osmium, and

cobalt have been reported, and the fragmentation pattern associated with

the structure of these polynuclear cornpound~.2~-~~

The study of the kinetics of substitution reactions of the Group

VI

carbonyls with a variety of phosphines, amines, and oligo-olefins have shown

that the reactions proceed by an

SNl

dissociative mechanism at low ligand

concentrations

(

<0.025~),53

whereas at higher concentrations

(>0.05~)

phosphine exchange occurs by a dual path involving an additional

SN2

mechanism.34 The kinetics

of

mono- and di-substitution of mcyclopenta-

dienylrhodium dicarbonyl by phosphines, phosphites, and isonitriles show

that the reaction is first-order

in

substrate and

a

reagent.35 The data on

the exchange of carbon monoxide and triphenylphosphine with nickel

carbonyl have been reassessed and indicate that the reaction proceeds

by

a

non-dissociative first-order process.

36

The structure

of

iron dodecacarbonyl has finally been resolved

in

the

solid state by X-ray diffraction, and is, as suggested in the previous

Annual

Reports,

a triangular metal cluster in which one bridging group of the

2s

S.

F.

A.

Kettle,

Spectrochim.

Acta,

1966,

22,

1388.

24

W. Beck,

A.

Melnikoff, and

R.

Stahl,

Chem. Ber.,

1966,

99,

3721.

25

A.

R.

Manning and

J.

R.

Miller,

J.

Chem.

SOC.

(A),

1966, 1521.

26

R.

W.

Cettrall and R.

J.

H.

Clark,

J.

Organometallic Chem.,

1966,

6,

167.

27

R.

E.

Winters and

R.

W.

Kiser,

J.

Chem. Phys.,

1966,

44,

1964.

28

B.

F.

0.

Johmon, J.

D.

Johnston, J. Lewis, and

B.

H.

Robinson,

Chem.

Comm.,

2s

J.

Lewis,

A.

R.

Manning,

J.

R.

Miller, and 5.

M.

Wilson,

J.

Chem.

SOC.

(A),

1966,

s1

B.

F.

G.

Johnson,

J.

Lewis, and

I.

G.

Williams,

Chem.

Comm.,

1966, 391.

8a

D.

W.

Slocum, R. Lewis, and

G.

J.

Mains,

Chem.

and

Ind.,

1966, 2095.

8a

H.

Werner and

R.

Prinz,

Chem. Ber.,

1966,

99,

3582;

J.

Organometallic Chem.,

84

R.

J.

Angelici

and

J.

R.

Graham,

J.

Amer.

Chem.

SOC.,

1966,88, 3658.

85

H.

G.

Schuster-Woldan, and

F.

Basolo,

J.

Amer. Chem. SOC.,

1966,

88,

1657.

86

L.

R. Kangas,

R.

F.

Heck,

P.

M. Henry,

5.

Breitschaft,

E.

M.

Thorateinson,

and

1966, 851.

1663.

R.

B.

King,

J.

Amer. Chem. SOC.,

1966,

88,

2075.

1966,

5,

79;

H.

Werner,

ibid.,

p.

100.

F.

Basolo,

J.

Amer. Chem.

Soc.,

1966,

88,

2334.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

KOHL

AND

LEWIS:

TRANSITION-METAL

CARBONYLS

211

Fe,(CO), system

is

replaced by an Fe(CO), The structure

of

a

related triphenylphosphine derivative, [Pe,( CO),1PPh,],39 has also been

determined; one

of

the terminal carbonyl groups

of

the E'e2(C0)g unit

ia

subktituted by the phosphine. The two bridging carbonyl groups arc

asymetrically bonded to the two iron atoms with iron-carbon distances

of

1.74

and

1.98A..

The structure

of

the hexapyridineiron salt

of

the ion

[Fe,(C0),,]2- has been determined by X-ray analysis; an Fe(CO), unit is

co-ordinated to a basal Fe,(CO), fragment with the remaining carbonyl

group bridging the three irons of the E"e,(CO)g group.4o The structure

of

the tetracobalt dodecacarbonyl has been shown to involve the co-ordination

of

a Co(CO), group to a plane

of

cO,(Co)g

in which three

of

the carbonyl

groups are bridging the three cobalt atoms in pairs.37 The corresponding

iridium compound was found to have no bridging carbonyl groups, whilst

the infrared spectra indicate that the corresponding rhodium complex has

a

similar structure to the cobalt complex.41 Baird and

Wilkinson

p2

have

shown that the sulphur analogue of carbonyl complexes may be obtained

from the reaction

of

carbon disulphide with rhodium and ruthenium

salts,

e.g.,

(Ph,P),Rh(

CO)Cl+

(Ph,P),Rh(

CS)Cl+

(Ph,P) ,Rh(

CS)Cl,.

The X-ray structure of the rhodium@) complex indicates a linear

rhodium-carbon-sulphur In contrast,

tetrakistriphenylphosphine-

platinum(

0)

reacts with carbon disulphide to give an addition complex

(Ph,P),PtCS, in which the platinum

is

considered to bond to the carbon

and one of the sulphur atoms.44

Carbonyls and Carbonyl Halides.-A

new low-pressure synthesis

of

ruth-

enium carbonyl from ruthenium chloride with zinc in methyl alcohol under

a

CO

pressure

of

less than

100

atmosphere is given.45 The reactivity

of

this

carbonyl with phosphines, nitric oxide, and organic dienes has been investi-

gated.4* With phosphines and dienes, trinuclear metal clusters occur in

the products, whilst in nitric oxide the

dinitrosyldicarbonylruthenium

is

formed.

A

range of technetium carbonyl adducts has been prepared with

phosphines, thiols, and halides as co-ordinated groups.47 Manganese penta-

carbonyl-nitrate has been shown to react with pyridine and bipyridyl to

give tricarbonyl adducts

in

which the nitrate group is still co-ordinated to

the metaL4* Anionic halogeno-rhenium carbonyl complexes have been pre-

pared and both mononuclear and binuclear systems have been isolated.49

cs,

c1,

s7

C.

H.

We;

and

L.

F.

Dahl,

J.

Amer. Chem.

SOC.,

1966,

88,

1821.

D.

J.

Dahm and

R.

A.

Jacobson,

Chem.

Comrn.,

1966, 496.

89

R.

J.

Angelici and

E.

E.

Siefert,

Inorg.

Chem.,

1966,

5,

1457.

40

R.

J.

Doedens and

L.

F.

Dahl,

J.

Amer. Chem.

SOC.,

1966,

88,

4847.

41

W.

Beck and

K.

Lottes,

Chem.

Ber.,

1961,

94,

2578.

42

M.

C.

Baird and

G.

Wilkinson,

Chem. Cornm.,

1966, 267.

43

J.

L.

De Boer,

D.

Rogers, A.

C.

Skapski, and

P.

G.

H.

Troughton,

Chem.

Comm.,

44

M.

C.

Baird and

G.

Wilkinson,

Chem. Comm.,

1966,

514.

46

M.

I.

Bruce,

F.

G.

A.

Stone,

Chem.

Cormn.,

1966, 684.

J.

P.

Candlin,

K. K.

Joshi, and D.

T.

Thomson,

Chem.

and

Id.,

1966, 1960.

W. Hieber,

F.

Lux,

and

C.

Herget,

2.

Nuturforsch.,

1965,

20b,

1159.

48

C.

C.

Addison and

M.

Kilner,

J.

Chem.

SOC.,

(A)

1966, 1249.

49

E.

W.

Abel,

I.

S.

Butter,

M.

C.

Ganorkar,

C.

R. Jenkins, and

M.

H.

B.

Stiddard,

1966, 756.

Inorg.

Chem.,

1966,

5,

25.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

212

INORGANIC CHEMISTRY

The reaction of carbon monoxide with hexachlororuthenate-(n) and

-(m)

yields

a

variety

of

anionic ruthenium carbonyl-halide derivatives.

50

The

formation

of

[Ru(CO)(H,O)C1J2- from ruthenium chloride and formic acid

has been studied kineti~ally.~~ The synthesis

of

the Rh(r) and Rh(m)

complexes trans-[RhX(CO)L,]

(X

=

C1,

Br,

I,

SCN;

L

=

PR,,

AsR,)

and

[Rh(CO)L,X,]

(X

=

C1, Br;

L

=

PR,)

is

reported. The rhodium(1) com-

pounds react with Ph2PCH,CH2PPh2 (diphos) to give the very stable

salt

Rh( diphos),Cl.

52

The corresponding cobalt complex

is

obtained from

the interaction

of

[Co(diphos),] and Co(diphos),X2,5S whilst the iridium

analogue is prepared from either the dicarbonyl-amine-halide complexes,

(CO),(amine)IrCl, with ph~sphine,~*

or

by the equivalent reaction used

for

the rhodium salt.54

In

the latter case the presence of a carbonyl inter-

mediate [Ir(diphos),(CO)]Cl has been detected. This compound may also

be prepared from the salt [Ir(diphos),]Cl with carbon monoxide.64 The

iridium salt reacts with oxygen to form [O,Ir(diphos),]Cl, and forms

six-

co-ordinate adducts with H,, HCl, HBr, H,S, and halogens, whilst five-

co-ordinate adducts are formed with

SO,

and

54

Oxidative addition

reactions of this type have been extensively reported for the iridium and

rhodium

d8

systems of the type

[L,M(CO)X]

(L

=

phosphine;

X

=

halogen),

to give L,M(CO)X,YZ

(M

=

Rh;

YZ

=

CH,COBr)

52

(M

=

fr; YZ

=

HF,

HC1, HBr,

HI,

H2S,55

RS02C1).56

[(

Ph,P),( CO)Cl,Ir( SO,R)], formed by this last reagent, lose sulphur dioxide

if

R

=

p-tolyl

or

phenyl, to give the aryl-iridium complex [L,Ir(CO)C1,R].56

With

boron

trihalides

57

for rhodium and sulphur dioxide

58

with iridium,

five-co-ordinate complexes are formed. The X-ray structure of the latter

compound [(Ph,P),Ir(CO)Cl(SO,)] has been determined and shows a tetra-

gonal bipyrimidal stereochemistry with bonding

of

the sulphur dioxide

through the s~lphur.5~ Tetracyanoethylene forms addition complexes with

both the rhodium and iridium series

as

also with the corresponding rhodium

thiocarbonyls [Rh(Ph,P),(CS)X] (X

=

Cl,

Br);

direct bonding

of

the olefin

group

is

postulated

to

occur in these complexes.g0

A

kinetic study of

the

addition

of

oxygen, hydrogen, and methyl iodide

to

the series

trans-

IrX(CO)(PPh,),

(X

=

Cl, Br,

I)

establishes that the reaction of hydrogen

and

oxygen is similar and differs from that of methyl iodide.61 The re-

markable nitrogen complex [(Ph,P),Ir(N,)Cl]

is

formed by the reaction

of

the

complex

[Ir(CO)Cl(PPh,),]

with

a

number

of

acid azides; a band at

2095

cm.-l

in the infrared spectrum is associated

with

the nitrogen-nitrogen

The iridium(=) X-sulphinates

J.

Halpern,

B. R.

James, and

A.

L.

W.

Kemp,

J.

Amer.

Chem.

SOC.,

1966,

88,

6142.

s1

J.

Halpern and

A.

L.

W.

Kemp,

J.

Amer.

Chem.

SOC.,

1966,

88,

5147.

52

J.

Chatt and

B.

L.

Shaw,

J.

Chem.

SOC.

(A),

1966,

1437.

63

A.

Sacco,

M.

Rossi, and

C.

F.

Nobile,

Chem.

Comm.,

1966, 589.

6*

L.

Vaskrt

and

D.

L. Catone,

J.

Amer.

Chem.

SOC.,

1966,88,

5324;

W.

Hisber and

6s

L.

Vaska,

J.

Amer.

Chem.

SOC.,

1966,

88,

6325.

s6

J.

P.

Collman and

W.

R.

Roper,

J.

Amer.

Chem.

SOC.,

1966,

88,

180.

57

P.

Powell and

H.

Noth,

Chm.

Comm.,

1966, 637.

18

L.

Vaska

and

S. S.

Bath,

J.

Amer. Chem.

SOC.,

1966,

88,

1333.

69

S.

J.

Laplaca and

J.

A.

Ibers,

Inorg.

Chem,

1966,

5,

405.

60

W.

H.

Baddley,

J.

Amer. Chem.

SOC.,

1966,88, 4546.

61

P.

B.

Chock and

J.

Halpern,

J.

Amer.

Chem.

SOC.,

1966,88, 9511.

V.

Frey,

Chem.

Ber.,

1966,

99,

2607.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

KOHL

AND

LEWIS

:

TRANSITION-METAL

CARBONYLS

213

stretching frequency.62 This complex is related to the nitrogen adducts

[(N,)Ru(NH,),]X, reported by Allen and Sen~ff,~, the X-ray structure of

which establishes a linear metal-nitrogen grouping.

64

A

polymeric carbonyl

halide of palladium, [PdCl(CO)],, has been obtained by passing moist air

through a suspension of PdC1,CO. The complex is a red-violet solid which is

insoluble in organic solvents.65

Nitrogen

and

Phosphorus

Derivatives.-The synthetic use

of

tris( aceto-

nitrile)tungsten tricarbonyl has been developed, and yields, with benzene,

toluene, p-xylene, mesitylene,

cyclohepta-1,3,5-triene,

cyclo-octadiene,

dimethylaminofulvene, the tricarbonyl adducts, whilst tetracarbonyl com-

plexes are formed with norbornadiene and cyclo-octa-l,5-diene, and a

dicarbonyl complex with cyclohexa-1,3-diene,

W(CO),(C6H,),.66

The photo-

chemical production

of

pentacarbonyl amine complexes

of

the Group

VI

carbonyls has been reported.67 Reactions

of

amines with molybdenum

pentacarbonyl-halogen anions, [Mo(CO),X]-, yield, in addition to the penta-

carbonyl amine complexes, the tetracarbonylbis( amine) adducts, the relative

proportions produced depending upon the halide anion involved.68

The

tetraethylammonium salts

of

the halogenopentacarbonyl anions

of

the

Group

VI

metals give mono-, bis-, and tris-isonitrile derivatives on reaction

with both alkyl and aryl i~onitriles.6~ Mixed phosphine

or

amine-bipyridyl

or

o-phenanthroline complexes of the form

M(

CO),X,Y and

M(

CO),X2Y,

[M

=

Cr,

Mo;

W,

X,

=

phen, bipy;

Y

=

py, NH,, Ph,P, (RO),P] have

been reported.'O Potassium cyanide reacts with the

(dicarbonyl)bis(bipyidyl)

complexes

of

chromium, molybdenum, and tungsten with displacement

of

the nitrogen bonds, to give the salts K4[M(C0)2(CN)4]

(M

=

Cr,

Mo,

W).'l

Octamethyltetraphosphonitrile

reacts with molybdenum carbonyl to give

a

fetracarbonyl phosphonitrile complex. The phosphonitrile is considered

to

bond

to the molybdenum through the two nitrogens at opposite ends

of

the

molecule

.71a

It

has been suggested that succinonitrile bonds to manganese by a

n-interaction

of

the cyano groups in the complexes

Mn(

CO),(NCCH,CH,CN)X

(X

=

C1,

Br,

I),72

whilst a normal a-bonding structure

of

the cyanide is

considered to occur

in

the acrylonitrile dimer, [(CO),Fe(CH,

=

CHCN)],.

The co-ordination number of the iron is attained by co-ordination

of

the

olefin group, the acrylonitrile acting as a bridging group between the two

metal ions.73 Nickel carbonyl reacts with diallylcyanamide

to

give the

dimer

[(

R,N*CN),Ni( CO)],

;

the structure

is

considered

to

involve bridging

62

J.

P.

Collman and

J.

W.

Kang,

J.

Amer. Chem.

SOC.,

1966,

88,

3459.

63

A.

D.

Allen and

C.

V.

Senoff,

Chem.

Comm.,

1965, 621.

64

F.

Bottomley and

S.

C.

Nyberg,

Chem.

Comm.,

1966, 897.

65

A.

Treiber,

Tetrahedron Letters,

1966, 2831.

*6

R.

B.

King

and

A.

Fronzaglia,

Inorg.

Chem.,

1966,

5,

1837.

67

W.

Strohmeier,

J.

F.

Guttenberger,

H.

Blumenthal, and

G.

Albert,

Chern.

Ber.,

68

H.

D.

Murdoch and

R.

Henzi,

J.

Organometallic

Chem.,

1966,

5,

463.

69

H.

D.

Murdoch and

R.

Henzi,

J.

Organometallic

Chem.,

1966,

5,

166.

70

L.

W.

Houk

and

G.

R.

Dobson,

Inorg.

Chem.,

1966,

5,

2119.

71

H. Behrens,

E.

Lindner,

and

J.

Rosenfelder,

Chem.

Ber.,

1966,

99,

2744.

'la

J.

Dyson and

N.

L. Paddock,

Chem.

Cmm., 1966, 191.

12

M.

F.

Farona and

N.

J.

Bremer,

J.

Amer. Chem.

SOC.,

1966,

88,

3735.

7s

E.

H.

Schubert and

R.

K.

Sheline,

Inorg.

Chem.,

1966,5, 1071.

1966,

99,

3419.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

214

INORGANIC CHEMISTRY

carbonyl groups with the two nitrogens bonding and the diallylcyanamide

acting as chelate.74 1,4-Diazabuta-l73-diene carbonyl complexes of nickel

and molybdenum have been obtained, and the reaction of these with iodine

and triphenylphosphine rep0rted.7~ The interaction of a series

of

new

phosphine ligands with metal carbonyls has been reported recently.

Tetrakis(diphenylphosphinomethy1)methane

reacts

as

a double bidentate

ligand with chromium, molybdenum, tungsten, and nickel carbonyls, to yield

the spirocyclic compounds

M(

GO),(

Ph,P*CH,), and

C(

CH,P.Ph,),M(

CO),

(M

=

Cr,

Mo,

W,

n

=

4;76 Ni,

n

=

2

77).

The nitrogen-phosphorus mixed

ligands Ph,PC,H,NEt,(NP), PhP(C,H,NEt,),(NPN), and

(Ph,PC,H,),NEt(PNP) react with molybdenum carbonyl to yield

Mo(CO),NP, Mo(CO),(NPN), and Mo(CO),(PNP),78 respectively, whilst the

potentially quadridentate group

tris-(o-diphenylphosphinopheny1)phosphine

(QP) reacts with manganese carbonyl compounds to give complexes

in

which the ligand is bidentate, [MnX(CO),(QP)] (X

=

halogen), terdentate,

[Mn(

CO),QP]+, or quadridentate,

[Mn(

CO),QP]

+.

The related ligands bis-

(o-dipheny1phosphino)phenylphosphine

(TP) and o-phenylenebisdiphenyl-

phosphine (DP) yield the complexes [Mn( CO),TP]+ and

[Mix(

CO),DP].'@

Oxidation

of [Mn(CO),(diphos),]Cl with a range of oxidising agents yields

the paramagnetic manganese(=) ion

[Mn(

CO),(diphos),]2+.

The first phosphine complexes of osmium carbonyl, Os(CO),(PPh,),, have

been isolated from the reaction

of

OsX,(CO),(PPh,), (X

=

halogen) with

zinc

in

the presence

of

CO.

The carbonyl-phosphine complex reacts with

halogens to give the ions [Os(CO),(PPh,),X]+

(X

=

Br,

I)

and hydrogen

chloride to give

[0s(CO),(C1,)(PPh3),].~~

The preparation of cationic car-

bony1 complexes, using the method of Fischer, Fichtel, and Oefele,82 has

been applied to rhodium and iridium carbonyl phosphine and stibene com-

plexes, to yield the ions [M(CO),L,]+

[M

=

Rh, Ir; L

=

PPh,, P(C,H,J,,

SbPh,].g3 With antimony, the hydrides HM(CO)(SbPh,),Cl,

(M

=

Rh,

Ir)

were also isolated.

A

series of phosphine-substituted products of nickel carbonyl with the

ligand 2,8,9-trioxa- l-phospha-adamantane,

P(

OCH,),(CH,),, have been

obtained. They are of the general formulae Ni(CO),-,L,

(x

=

1,2,3,4).

With iron, chromium, molybdenum, and tungsten, the corresponding mono-

and di-substituted compounds were obtained. The reactions

of

nickel

carbonyl with the series of bifunctional phosphines

(CF,)2POP(CF,)2,

(CF,),PSP(CF,),, and (CF,),PN(Me)P(

CP3),

lead to polymers involving

bridging carbonyl groups.s5

74

H.

Bock and

H.

tom Dieck,

Chem. Ber.,

1966,

99,

213.

75

H.

Bock and

H.

tom Dieck,

Angew. Chem.,

1966,

78,

549.

76

J.

Ellermann and

K.

Dorn,

J.

Organometallic Chem.,

1966,

6,

157.

77

J.

Ellermann and

K.

Dorn,

Angew. Chem.,

1966,

78,

547.

78

G.

R.

Dobson,

R.

Craig Taylor, and T. D. Walsh,

Chem.

Comm.,

1966, 281.

79

B.

Chiswell and

L.

M.

Venanzi,

J.

Chem. SOC.

(A),

1966, 417.

80

M.

R.

Snow and

M.

H.

B.

Stiddard,

J.

Chem.

SOC.

(A),

1966, 777.

81

J.

P.

Collman and

W.

R.

Roper,

J.

Amer. Chem.

SOC.,

1966,

88,

3504.

8a

E.

0.

Fischer,

K.

Fichtel, and

K.

Ofele,

Chem.

Ber.,

1962,

95,

249.

83

W.

Hieber and V. Frey,

Chem. Ber.,

1966,

99,

2614.

84

D.

G.

Hendricker,

R.

E. McCarley,

R.

W.

King,

and

S.

G.

Verkade,

Inorg.

Chem.,

1966,

5,

639.

86

A.

B.

Burg

and

R.

A.

Sinclair,

J.

Amer. Chem.

SOC.,

1966,

88,

5354.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

KOHL

AND

LEWIS

:

TRANSITION-METAL

CARBONYLS

215

Sulphur

Derivatives.-The interaction of molybdenum and tungsten car-

bonyls with nickel bis(dithioketone) yields the a-dithioketone complexes

M(S,C,R,)(CO),

(M

=

W,

R

=

Me) and M(S,C,R,),(CO),

(M

=

Mo,

W,

R

=

alkyl

or

aryl); the reactivity of the carbonyl groups in these molecules

to phosphine molecules has been investigated.86 The investigation of the

reactions of thiols with rhenium and manganese carbonyl complexes has

continued,*',

88

and the field has been extended with the formation

of

the

corresponding selenium

ad duct^.^^

A

series of manganese carbonyl derivatives of dithiocarbonates and

monothiocarbonates has been reported 00'-dimethyl and -diphenyl

dithiophosphate complexes of manganese carbonyl have been studied, and

in the bipyridyl complexes

Mn(

CO),(

bipy)

(

S,P(OR),

the ligand appears to

be acting as a unidentate rather than a bidentate gro~p.~l The product of

the reaction

of

bis(trifluoromethy1)dithietin

with the cobalt carbonyl has

been established to be trimeric [C,F,S,Co(CO)], from the mass spectra.

The complex is paramagnetic

(p

=

1-84

B.M.)

as anticipated on this formula-

tion. The isoelectronic nitrosyl iron compound has also been shown to be

trimeric

from

the mass spectra, [E"e(NO)C,F6S,],.92

Miscellaneous.-The preparation

of

compounds with boron-manganese

bonds has been rep0rted.~3 Bisdimethylaminoboron chloride reacts with

sodium manganesepentacarbonyl to give the compound (Me,N),B-lSh(CO),.

The complex reacts with hydrogen at

100

atmospheres to give manganese

carbonyl and bis( dimethylamino)borane, and with bromine to yield bis-

(dimethy1amino)boron bromide and pentacarbonylmanganese bromide. The

IIB

n.m.r. spectra are interpreted.

as

indicating back-donation from the

manganese d-orbitals to the trigonal planar boron atom.

A

series of tri-

phenylphosphine oxide and bipyridyl dioxide complexes

of

rhenium carbonyl

halides is reported.94

Hydrides.-The formation

of

bis-

(n-cyclopentadieny1)zirconium

dihydride

and the monohydride-borohydride adduct is reported

to

occur

by

action of trimethylamine on the corresponding borohydride complex

(n-C,H,),Zr(BH,),. The complexes are postulated

to

have a polymeric

bridging hydride structure

S5

with the metal-hydrogen vibration occurring

at

1540

cm.-l. The reaction of nitrogen with transition-metal complexes

to give ammonia has been establi~hed.~6

For

the system

(n-C,H,),TiCl,-C,H,MgX, the e.s.r. spectra have been interpreted

as

indi-

86

G.

N.

Schrauzer,

V.

P.

Mayweg, and

W.

Heinrich,

J.

Amer.

Ohm.

Soc.,

1966,

88,5174;

G.

N. Schrauzer,

V.

P.

Mayweg,

H.

W. Finck, and

W.

Heinrich,

ibid.,

p.

4604.

87

A.

G.

Osborne and

F.

G.

A.

Stone,

J.

Chem. SOC.

(A),

1966, 1143.

88

E.

W. Abel and

B.

C.

Crosse,

J.

Chern.

SOC.

(A),

1966, 1141.

8g

E.

W.

Abel,

B.

C.

Crosse, and

G.

V.

Hutson,

Chem. and

Id.,

1966,238.

go W.

Hieber and

M.

Gscheidmejer,

Chem. Ber.,

1966,

99,

2312.

O1

F.

A.

Hartman and

A.

Wojcicki,

Inorg.

Nuclear Chem.

Lettes,

1966,

2,

303;

g2

R.

B.

King

and

F.

T.

Korenowski,

Chem. Comm.,

1966, 771.

CJ*

H.

Noth and

G.

Schmid,

J.

Organometallic

Chem.,

1966,

5,

109.

O4

U.

Sartorelli,

F.

Canziani,

and

F.

Zingales,

Inorg.

Chem.,

1966,

5,

2233.

96

B.

D.

James,

R. K.

Nanda, and

M.

G.

H. Wallbridge,

Chem.

Cm.,

1966,

849.

CJ6

M.

E.

Vol'pin and

V.

B.

Shur,

Nature,

1966,209,1236;

M.

E.

Vol'pin,

V.

B.

Shur,

K.

N.

Latyaeva,

L.

J.

Vyshinskays,

A.

L.

Shul'gaitser,

Izvest. Akad. Nauk

S.S.S.R.

Ser. khim.,

1966, 385.

R.

L.

Lambert and

F.

A.

Manuel,

Inorg.

Chem.,

1966,5, 1287.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

216

INORGANIC CHEMISTRY

cating the presence

of

binuclear hydride bridges with nitrogen insertion

into those hydride bonds with formation

of

imine

specie^.^'

The wide-line n.m.r. spectrum of the manganese pentacarbonyl hydride

indicates that the

H-Mn

bond distance

is

1*28A,

and hence establishes

the presence of

"

short

"

metal-hydrogen bonds in these sy~tems.~g

The preparation and reactions

of

hydrido

t

e

tracarbon

yl

t

rip hen ylp hosp hine

-

manganese(@ has also been reported.99 The X-ray structures

of

the

ion [Cr,H(CO),,]- have been interpreted

in

favour

of a linear Cr-H-Cr

group.100 The synthesis

of

[M,H(CO),,]- and [M2(CO),o]2-

(M

=

Cr,

Mo,

and

W),

and the intercorrelation between the two

sets

of

ions, has been

established

;

the formation

of

mixed complexes

[MM'H(CO),,]-

has been

detected from the n.m.r. spectra, and the infrared and 11.111.13. data

on

the

series interpreted in terms of a symmetrical hydrogen-metal bridge.101 The

addition

of

the Lewis acids

BF,

and

BCI,

to bis mcyclopentadienyl hydrides

of molybdenum, tungsten, and rhenium leads to the formation

of

1

:

1

adducts.lo2

A

new polynuclear hydride

of

rhenium HRe,(CO),, has been

reported

lo1

and the exchange of

13C0

with

the hydride studied; this

enables the preparation of stereospecific

13C0

labelled Re,(CO),, to be

obtained.lo1

A

comprehensive study

of

the rhenium hydride phosphine

system has been carried

and yields three classes

of

compounds,

ReH,(PR,),, [ReHz(PR3)2]n, and [ReH,(PR,),].

A

nitrosyl hydride

of

iron HFe(NO)(PF,), has been obtained by acidification of the potassium

salt prepared by the action

of

potassium amalgam on the dinitrosylbis-

trifluorophosphineiron complex.

lo4

Three new ruthenium hydrocarbonyls have been obtained, H,Ru,(CO),,

and

H2Ru,(C0),,.28,

lo5

The first compound appears to exist in two different

forms, as the proton n.m.r. signals occur at

z

18.5

and

23.5

for the two

isomers. The hydrogen-metal stretching vibration in some iridium

and

osmium carbonyl hydridophosphine complexes have been shown to be

coupled to the carbonyl vibration when the hydrogen is

trans

to

the carbonyl,

but

no

interaction occurs in the cis-compounds.lo6 Some hydrido-complexes

of iridium(@ with trichlorotin and a variety of phosphine ligands have been

reported.

107

The first pure hydrido- complexes with only non-n- bonding

ligands co-ordinated to the metal have been obtained by the zinc-dust

reduction of

chloropenta-amminerhodium(m)

salts,1°8

in

the anions

[RhH(NH,),]2+

and

[RhH(H20)(NH,)J2+.

A

related cyanide complex,

K,[RhH(CN),(H,O)], has been obtained from rhodium carbonyl chloride

07

H.

Brintzinger,

J.

Amer. Chem.

SOC.,

1966,

88,

4305,

4307.

98

T.

C.

Farrar,

W.

Ryan,

A.

Davison, and

J.

W.

Faller,

J.

Amer.

Chem.

SOC.,

1966,

99

B.

L.

Booth

and

R.

N.

Haszeldine,

J.

Chem.

SOC.

(A),

1966, 157.

88,

184.

100

L.

B.

Handy and

P.

M.

Treichel,

J.

Amer. Chem.

SOC.,

1966,

88,

366.

101

R.

G.

Hayter,

J.

Amer. Chem.

SOC.,

1966,88,4376;

R.

W.

Hamil

and

H.

D.

Kaesz,

102

M.

P.

Johnson

and

D.

F.

Shriver,

J.

Amer. Chem.

SOC.,

1966, 88, 301.

lo3

J.

Chatt and

R.

S.

Coffey,

Chem. Comm.,

1966, 545.

lo4Th.

Kruckand

W.

Lang,

Chem. Ber.,

1966,

99,

3794.

105

J.

W.

S.

Jamieson,

J.

V.

Kingston, and

G.

Wilkinson,

Chem.

Cmm.,

1966, 569.

L.

Vaska,

Chem. Comm.,

1966;

J.

Amer. Chem.

SOC.,

1966,88,4100.

107

R.

C.

Taylor,

J.

F.

Young,

and

G.

Wilkinson,

Inorg.

Ch.,

1966,5,

20;

A.

Sacco,

168

J.

A.

Osborn,

A.

R.

Powell, and

G.

Wilkinson,

Chem. Comm.,

1966,

461.

Inorg. Nuclear Chem. Letters,

1966,

2,

69;

W.

Fellmann and

H.

D.

Kaesz,

ibid.,

p.

63.

R.

Ugo,

and

A.

Moles,

J.

Chem.

SOC.

(A),

1966, 1670.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

KOHL

AND

LEWIS

:

TRANSITION-METAL

CARBONYLS

217

and cyanide

;

the compound reacts with nitric oxide, tetrafluoroethylene,

and oxygen to give K,[Rh(CN),(NO,)H,O], K3[Rh(CN)5C2F4H], and

K4[

(CN),(

H20)Rh0,Rh( CN),( H,O)], respectively.

lo9

A

series

of

equilibria

l10

have been established between zerovalent

platinum phosphine complexes and hydrido-phosphine complexes on reaction

of the

tetrakistriphenylphosphineplatinum(0)

and tristriphenylphosphine-

platinum(0) complexes with acids

(L

=

triphenylphosphine).

-L

HC1

-L

PtL, PtL, \k[PtHL,]Cl [PtHClL,]

+L

-TICXI

lHCl

+L

KOH

Ik

[PtH,C1,L,I

Using

110

this system,

it

has been possible to isolate a series of derivatives

of

the type [PtH(PPh,),]X (X

=

ClO,-,

BF4-,

HS04-,

CH,0S03-) and

[PtHY(PPh,),]

(Y

=

CN-,

SCN-).

The reaction

of

the complex

[PtH(PPh,),]HSO, with base in the presence of oxygen produces the zero-

valent

bistriphenylphosphineplatinum

compound,lll [Pt(PPh,),]. The bis-

phosphine chlorohydride platinum complex has been shown to react with

tetracyanoethylene to give the first example

of

a

carbon, with

a

cyanide

group attached, bonding directly to a metal, (Ph,P),Pt(C6N,).ll2

During the past year, continued interest in homogeneous hydrogenation

using transition-metal complexes as catalysts has been maintained.

An

extensive discussion of the kinetics and mechanism of these reactions using

the complexes (Ph,P),RhX (X

=

C1,

Br,

I)

as catalysts has been given,113

and the activity of the related compounds (MPh,),RhCl

(M

=

As,

Sb)

assessed.ll4

Por

the system (PtCl,C,H,), it is concluded that hydrogenation

of

the n-bonded ethylene occurs without the formation of a-diadsorbed

intermediates.ll5 The homogeneous hydrogenation

of

aldehydes has been

accomplished under hydroformylation conditions using

a

rhodium trichloride

catalyst

;

rhodium carbonyl compounds are possible intermediates in this

process.lls The kinetics and mechanism of the homogeneous catalytic

hydrogenation of maleic and fumaric acids with a ruthenium(=) chloride

catalyst has been studied. Tracer studies indicate that the hydrogen atoms

added to the olefin group originate from the solvent rather than the hydrogen

gas.ll7

Nitrosyls.-The

e.s.r.

spectra

of

the metal pentacyanonitrosyl complexes

of

some of the first-row transition elements have been discussed.llg The

infrared spectra of various metal nitrosyl complexes

119

have been measured

loB

D.

N.

Lawson, M.

J.

Mays, and

G.

Wilkinson,

J.

Chem.

Soc.

(A),

1966,

52.

110

F.

Cariati,

R.

Ugo,

and

F.

Bonati,

Inorg. Chem.,

1966,

5,

1128.

ll1

R.

Ugo,

F.

Cariati, and

G.

La Monica,

Chem.

Comm.,

1966, 868.

112

W. H. Baddley and

L.

M.

Venanzi,

Inorg. Chem.,

1966,

5,

33.

119

J.

A. Osborn,

F.

H. Jardine, J.

F.

Young,

and

G.

Wilkinson,

J.

Chem.

SOC.

(A),

J.

T.

Mague and

G.

Wilkinson,

J.

Chem.

SOC.

(A),

1966, 1736.

115

K.

E.

Hayes,

Nature,

1966,

210,

412.

ll6

B.

Heil and

L.

Mark6,

Chem. Ber.,

1966,

99,

1086.

11'

J. Halpern,

J.

F.

Harrod, and

B.

R. James,

J.

Amer.

Chem.

Soc.,

1966,

88,

6150.

P.

T.

Manoharan and

H.

B.

Gray,

Incrg. Chem.,

1966,

5,

823;

B.

A. Goodman,

11*

P.

Gans,

A.

Sabatini, and

L.

Sacconi,

Inorg. Chem.,

1966,

5,

1877.

1966, 1711.

J.

'€3.

Raymor, and M.

C.

R.

Symons,

J.

Chem.

SOC.,

(A)

1966,

994.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

218

INORGANIC

CHEMISTRY

between

4000

and

80

cm.-l. The approximate nitrosyl and carbonyl

force constants have been calculated

for

the isoelectronic series Mn(NO),CO,

Fe(NO),(CO),, Co(NO)(CO),, and Ni(CO),, and the variation of these values

for

the substituted derivatives LMn(NO),, Ni(CO),L,, Fe(NO),L,, and

Co(NO)L, discussed in terms

of

the n-bonding properties

of

the group L.120

The presence

of

considerable n-bonding between nitrogen and chromium in

the complex ~-C,H,Cr(NO),Cl has been deduced from the X-ray structure

of

the compound.121 The presence

of

geometrical isomers

of

the series

[C5H5Cr(NO)XI2 [X

=

NMe,,

SR;

(Y-PeSMe),,

Y

=

(CO),, (NO),],

[C,H,NiX],

(X

=

SMe), and [C,H,Fe(CO)X], (X

=

SR,

PPh,) has been

established,12, and their separation achieved.

Nitrosyl-iron and -cobalt

adducts

of

the ligands [S,C,R,] (R

=

C,H,, CF,, CN) have been isolated.l23

A

series

of

octahedral nitrosyl ruthenium complexes

of

the type Ru(NO)X,L,

has been reported

(X

=

halogen;

L

=

pyridine, CH,CN, R,As, R,Sb, R2S,

bipy, phen, diar~ine).12~

Both five-co-ordinate and six-co-ordinate binuclear

complexes (NO)RuI,X,

(X

=

pyridine, bipy, R,As) have been prepared.125

The X-ray structure

of

the alleged seven-co-ordinate complex

(NO)Ru(S2CNEt,), shows

it

to be six-co-ordinate, with one

of

the dithio-

carbonate groups being bonded as

a

unidentate group.l26

Reaction of the

compounds Co(NO)(CO), and Fe(NO),(CO), with excess

of

diphos established

the presence

of

''

long lived

"

intermediates with the phosphine bonded

through only one phosphorus atom, which react finally to give the disub-

stituted derivatives. The diphosphine has been shown to act as

a

bridging

group12' between two [Co(NO)(CO),] groups, and on reaction with both

carbonyls forms the mixed complex (NO),Fe( C0)-diphos-Co( CO),(NO).

In the complex

C1(NO),Co-diphos-Co(NO),C1

a similar diphos bridge

is

present. Binuclear phosphido-bridged adducts, [(NO),M-PPh,],

(M

=

Fe,

Co)

have also been obtained.l28?

lZ9

A

series

of

cyanonitrosyl and cyano-

carbonylnitrosyl anions

of

cobalt has been prepared from the reaction

of

potassium cyanide with

nitrosyltricarbonylcobalt

in

liquid ammonia.130

The kinetics and mechanism

of

the reactions

of

a variety

of

phosphines,

phosphites, arsines, isonitrile, and pyridine derivatives with the complex

[NOCo(CO),] have been elucidated,131 and the products [Co(NO)(CO),L]

is01ated.l~~

A

large range

of

mono- and di-nitrosyl complexes

of

cobalt with

lao

Q.

R.

van

Hecke

and W.

Dew,

Inorg.

Chem.,

1966,

5,

1960.

lal

0.

L.

Carter,

A.

T.

McPhail, and

G.

A. Sim,

J.

Chem.

SOC.

(A),

1966, 1095.

laa

M.

Ahmad,

R.

Bruce, and

G.

Knox,

2.

Naturforsch.,

1966,

216,

289.

lP8

J.

Locke,

J.

A.

McCleverty,

E.

J.

Wharton, and

C.

J.

Winscom,

Chem. Comm.,

la4

J.

Chatt

and B.

L.

Shaw,

J.

Chem.

SOC.,

1966, 1811;

M.

B. Fairy and

R.

J.

Irving,

mi

R.

J.

Irving

and

P.

G.

Laye,

J.

Chem.

SOC.

(A),

1966, 161.

18*

A.

Domenicano,

A.

Vaciago,

L.

Zambonelli,

P.

L.

Looder,

and

L.

M.

Vemmzi,

la'

R.

J.

Mawby,

R.

Morris, and

E.

M.

Thorsteinaon, and

F.

Basolo,

Inorg.

Chem.,

128

W.

Hieber

and

G.

Neumair,

2.

anorg.

Chem.,

1966,

342,

93.

lze

W. Hieber and

R.

Kummer,

2.

anorg.

Chem.,

1966,

344,

292.

l9O

H.

Behrens,

E.

Lindner,

and

H.

Schindler,

Chem.

Ber.,

1966,

99,

2399.

ls4

E.

M.

Thorsteinson

and F. Basolo,

Inorg.

Chern.,

1966,

5,

1691.

1966, 677.

ibid.,

p.

475.

Chem.

Cmm.,

1966,476.

1966,

5,

27.

E.

M.

Thorsteinson and

F.

Basolo,

J.

Amer.

Chem.

SOC.,

1966,

88,

3929.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

KOHL

AND

LEWIS:

TRANSITION-METAL CARBONYLS

219

ethylenediamine, pyridine, and aniline as ligands has been e~tablished,l~~-l~~

and the nature

of

the nitrosyl group in theredand black penta-ammine cobalt

salts discussed.135

Transition-metal Carbonyl Complexes

containing

Metal-Metal Bonds.-

An

electrochemical study

of

a

large range of compounds containing

metal-metal bonds has been reported, and the nucleophilicities of some

transition-metal complex anions studied.136 The metal-metal bond energy

in

manganese decacarbonyl has been determined

137

to

be

18.9

&

1.4

kcal.

from mass-spectral data; this value falls near the range

34

&

13

kcal.

determined earlier.138 Raman spectroscopy has been applied

to

some

binuclear metal carbonyl complexes, and shows that the approximate

force constants

of

the decacarbonyls

M2(C0)10

follow the order

Re-Mn

>

ReRe

>

Mn-Mn.139 The infrared spectra of manganese deca-

carbonyl and the bisphosphine substituted complexes

l4O9

141

have been

discussed in terms

of

the

Cotton-Kraihanzelm0de1.~4~

The data imply that

there

is

no n-bonding across the metal-metal bond.l4l

The triphenyl-

phosphine-manganese decacarbonyl system

has

been reinvestigated, and the

adducts isolated are (Ph,P)Mn,(CO), and [(Ph,P)Mn(CO),],. The presence

of a monomeric paramagnetic species, [(Ph,P)Mn(CO),], has been refuted.143

However, the kinetics

of

the reaction

of

Ph,P

with iodine and manganese

decacarbonyl indicate that the primary step is

fission

of

the metal-metal

bond to give

Mn(CO),

radicals.ld4 The kinetics

of

carbon monoxide exchange

of a variety

of

carbonyls containing Hg-Co, Cd-Co, Sn-Coy Au-Coy and

Au-Mn bonds have been carried and the rate

of

exchange is found

to

vary widely. Anisotropic electron-transport has been established in single

crystals

of

the complexes Ir(acac)(CO), and Rh(aca~)(CO)~ (acac

=

acetyl-

acetonate ion). Maximum electrical conductivity occurs along the axes

of

the metal-metal bonds.l*6

The structure of the compound

(

C,H5C,C6H,)Fe,(CO)g involves a triangle

of iron atoms each with three terminal carbonyl groups. The organic group

is situated above this plane with one

of

the acetylenic carbon atoms bonded

to

all the iron atoms, whilst the other acetylene carbon is bonded to

only

two of the iron atoms.147

A

new osmium dodecacnrbonyl complex, with

133

W. Beck, W. Hieber, and

G.

Neumair,

2.

anorg.

Chem.,

1966,

344,

285.

13p

T.

B. Jackson,

M.

J.

Baker,

J.

0.

Edward,

and

D.

Tutas,

Inorg.

Chern.,

1966,

136

J.

B.

Raynor,

J.

Chem.

SOC.

(A),

1966, 997.

13$

R.

E.

Dessy,

P.

M.

Weissman,

and

R.

L.

Pohl,

J.

Amer.

Chem.

SOC.,

1966,

88,

5117;

R.

E.

Dessy,

R.

B.

King,

and

M.

Waldrop,

ibid.,

p.

5112;

R.

E. Dessy,

F.

E.

Stary,

R.

B. King, and

M.

Waldrop,

ibid.,

p.

471.

137

D.

R.

Bidinosti and

N.

S.

McIntyre,

Chem.

Comm.,

1966,

555.

13*

F.

A.

Cotton and

R.

R.

Monchamp,

J.

Chem.

Soc.,

1960,

533.

lBD

H.

M.

Gager,

J.

Lewis,

and

M.

J.

Ware,

Chem. Comm.,

1966, 616.

14*

D.

J.

Parker and

M.

H.

B.

Stiddard,

J.

Chem.

Soc.,

1966, 695.

141

J.

Lewis,

A.

R.

Manning,

and

J.

R.

Miller,

J.

Chem.

SOC.

(A),

1966, 845.

Ira

F.

A.

Cotton and

C.

S.

Kraihanzel,

J.

Amer.

Chem.

SOC.,

1962,

84,

4432.

lr3

H.

Wawersik

and

F.

Basolo,

Chem.

Comm.,

1966, 366.

144

D.

Hopgood,

and

A.

J.

Po6,

Chem.

Cmnm.,

1966, 831.

145

S.

Breitschaft and

F.

B~olo,

J.

Amcr.

Chent.

SOC.,

1966,

88,

2702.

146

C.

G.

Pilt,

L.

K.

Monteith,

L.

F.

Ballard,

J.

P.

Collman,

J.

C.

Morrow,

W.

R.

14'

J.

F.

Blount,

L.

F.

Dahl,

C.

Hoogzand, and

W.

Hiibel,

J.

Amer.

Chem.

SOP.,

88,

2046.

Roper,

and

D.

Ulkii,

J.

Amer.

Chem.

Soc.,

1966, 88,4236.

1966,

88,

292.

xi

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

220

INORGANIC

CHEMISTRY

osmium tetroxide

is

reported, OS,(CO)~~,OSO~, and is considered to involve

bonding

of the

OsO,

group through three oxygens to the plane of osmium

atoms.148

A

silicon analogue of the dimer [Co,(CO),C], has been prepared

by

the reaction

of

tetraphenylsilane with cobalt carbonyl, and

is

the fist

cazbonyl reported

149

with a silicon-silicon bond, [Co,(CO),Si],

.

The prepara-

tion

of

the complex [Co(CO),],C .CH2CH2C0,H

is

reported.l5*

The X-ray

structure

of

bis(tricoba1t enneacarbonyl)acetone, obtained by heating the

compound [Co(CO),],CBr to

90°c,

shows that insertion of a carbonyl

group

between the two carbon atoms of the dimers to give

is involved.151 The interaction

of

3,3,3-trifluoropropyne with cobalt carbonyl

has

been investigated,162 and the complexes [Co(

CO)3],C*CH2CF,

(I),

[Co(CO),],HC*C*CF,

(11),

and [Co(CO),],[HC*C*CF,],

(111)

have been isolated.

Compound

(I)

is considered to be a derivative of the [Co,(CO),C] cluster;

(11)

is related to the corresponding complex of hexafluorobut-2yne

[(cF,c=cc~,)co,(co)6],153

whilst

(111)

is postulated to have bridging

oleh groups. The preparation of a new type of metal cluster with manganese

and iron carbonyls has been reported in the ion [MIIF~,(CO)~,]-,~~~ and the

compound [Mn,Fe(CO)l,]

.lS5

The crystal structure

of

the complex

n-C,H,Fe(CO),Mn(

CO),

has been determined and shows that the molecule

contains a metal-metal bond.156 The preparation

of

the mixed carbonyls

(CO),Re-Mn(CO),, (CO),Re-Co(CO),, and some derivatives has been effected

by

a

Wurtz-type reaction between anionic and cationic carbonyl species.

l5'

A

bidentate gold ligand, Ph,P*AuC,H4C6H4Au*PPh2, has been used to pre-

pare the first chelate complex containing metal-metal bonds, by interaction

of the ligand with the anion l?e(CO),2-.158 Cationic complexes in which

mercury

is

bonded to iron,lS9 ruthenium, and osmium

l60

carbonyl phosphine

derivatives have been reported. For the iron complex, the stability of the

product depends upon the nature

of

the phosphine.

For

ruthenium and

osmium the compounds are formulated

as

[(

CO),M

L,(HgX)][HgX,],

(L

=

Ph,P,

X

=

C1,

Br,

I;

M

=

Ru,

0s).

Substitution reactions of the

compounds (XHg),Fe(CO),

(X

=

CJ,

Br),

with a variety of nitrogen bases

have been studied.161 The interaction

of

mercuric chloride with cyclo-

391.

L.

Marko,

and

B.

Marko,

Chem.

Ber.,

1962,

95,

333.

14*

B.

F.

G.

Johnson,

J.

Lewis,

I.

0.

Williams,

and

J.

Wilson,

Chm.

Comm.,

1966,

149

S.

F.

A.

Kettle and

I.

A. Khan,

J.

Organometallic Chenz.,

1966,

5,

588;

M.

G.

Bor,

150

G.

Albanesi and

E.

Garezotti,

Chimica e Industria,

1965,

47,

1322.

151

G.

Allegra,

E.

M.

Peronaci, and R. Ercoli,

Chem.

Comm.,

1966, 549.

152

D.

A.

Harbourne,

D.

T.

Rosevear, and

F.

0.

A. Stone,

Inorg. Nwbar Chem.

Letters

153

154

156

158

157

158

159

160

16

1

I,

1966,

2,

247.

J.

L.

Boston,

D.

W.

A.

Sharp, and

G.

Wilkinson,

J.

Chem.

SOC.,

1962, 3488.

U.

Anders and

W.

A.

G.

Graham,

Chem.

Comm.,

1966, 291.

E.

H.

Schubert and R.

K.

Sheline,

2.

Naturforsch.,

1965,

206,

1366.

P.

J.

Hansen and

R.

A.

Jacobson,

J.

0,rganometallic

Chem.,

1966,

6,

389.

Th.

Kruck,

M.

Hofler,

and

M.

Noack,

Chem. Ber.,

1966,

99,

1153.

B.

Chiswell and

L.

M.

Venanzi,

J.

Chem.

SOC.

(A),

1966, 901.

D.

M.

Adam,

D.

J.

Cook, and

R.

D.

W.

Kemmit,

Chem. Comm.,

1966, 103.

J.

P.

Co1lma.n and

W.

R. Roper,

Ch.

Comm.,

1966, 244.

J.

Lewis

and

S.

B.

Wild,

J.

Chem.

SOC.

(A),

1966,

69.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

KOHL

AND LEWIS: TRANSITION-METAL CARBONYLS

221

pentadienylcobalt dicarbonyl162 yields the ionic complex

[Co(CO),(C,H,)HgCl]Cl related to the phosphine carbonyl derivatives

of

osmium and ruthenium discussed above.

A

wide range

of

tin-metal bonds has been prepared.

A

new preparative

technique

for

the interaction

of

amido-tin complexes with transition-metal

hydrides has been developed, and leads to the complexes (Ph,P),PtCl( SnMe,)

and

(

C,H,)

(CO),W-SnMe,.

C,H,(CO),Mo*Ti(OPri),, has been obtained using the same type of rea~ti0n.l~~

The reaction

of

the anions

[M(C,H,)(CO),]-

(M

=

Cr,

Mo,

W)

with the com-

pounds

R,MX

(M

=

Ge, Sn, Pb;

R

=

Me, Ph;

X

=

halide) yields the

complexes

[C,H,(

C0),M-M'R3]. The stability

of

these clusters increases

from chromium to tungsten.16, The preparation and spectroscopic pro-

perties

of

the series Ph,M'-M(CO),

(M'

=

Si, Ge, Sn, Pb;

M

=

Mi,

Re) and

X,Sn-M(CO),

(M

=

Re,

Mn,

X

=

Me,

C1,

Br) have been investigated.

It

is concluded that in these compounds the Br,Sn- and C1,Sn- groups are

strong n-acceptor ligands.

l65

The X-ray structure

of

the compound

Ph,Sn-Mn(CO), is reported.lG6 The reaction

of

iron pentacarbonyl with

tributyltin chloride yields the compounds [BuaSnFe(C0),],Fe(CO),,

Bu,Sn,[Fe(CO),],, and Sn[Fe(CO)J,; the last compound may be obtained

directly

from

stannous chloride and iron carbonyl. The X-ray structure

of

this compound indicates a tetrahedral array

of

iron atoms around the tin,

each

iron

having

four

terminal carbonyl groups and the iron atoms

being

bonded to each other in pairs.167 The preparation and infrared spectra

of

the complex RSn[Co(CO),],

(R

=

Ph, Me, CH,

=

CH,

n-C4H5, C1, Br,

I)

have been reported.16s Interaction

of

rhodium and iridium carbonyl phos-

phines, [L,M(CO),], with sodium amalgam in the presence

of

carbon monoxide

and subsequent addition

of

trimethyltin halide, triphenylphosphinegold

halide,

or

mercuric cyanide gives the compounds [Me,SnM(Ph,P)(CO),],

[Ph,PAuIr(CO),Ph,P], and [Ph,P*Ir(CO),],Hg,

(M

=

Ir, Rh)

.169

The use

of

insertion reactions for the preparation

of

metal-metal

bonds has been applied to give the complexes [C,H5Fe(CO)2],SnC1,,170

[(CO),LCo],SnX,

[X

=

C1,

Br, I;

L

=

CO, Ph,P, (PhO),P, BU,P],~~~,

172

and

[C5H,(CO)Ni],SbC1,,171 when stannous halides are used. Other Group

I11

or

IV

halides can also participate in insertion reactions, and thus the compounds

[C,H,Fe(CO),],GeI,,

[Co(

CO),],InBr,THF, and XGa[Co(CO),],,

THF

(X

=

Br,

I)

172

have been prepared. The germanium compound may react

with methyl-lithium or borohydride to give the adducts X,Ge[Co(CO),],

A

molybdenum-titanium complex,

162

D. J.

Cook

and

R.

D.

W.

Kemmitt,

Chern.

and

Ind.,

1966, 946.

163

D.

J.

Cardin and

M.

F.

Lappert,

Chem. Comm.,

1966,

506.

164

H.

R.

H.

Patil and

W.

A.

G.

Graham,

Inorg.

Chem.,

1966,5, 1401.

166

W.

Jetz,

P.

B.

Simons,

J.

A.

J.

Thompson,

and

W.

A,

G. Graham,

Inorg.

Chm.,

16'

J.

D.

Cotton,

J.

Duckworth,

S.

A.

R.

&ox,

P.

F.

Lindley,

I.

Paul,

F.

G.

A.

Stone,

169

J.

P.

Collman,

F.

D.

Vastine, and

W.

R. Roper,

J.

Amer.

Chem.

Xoc.,

1966,

88,

170

C.

Edmondson and

M.

J.

Newlands,

Chern.

and

Ind.,

1966, 1888.

171

D.

J.

Patmore

and

W.

A.

G.

Graham,

Inorg.

Chem.,

1966, 5, 1405.

1966, 2217.

H.

P.

Weber

and

R.

F.

Bryan,

Ch.

Comm.,

1966,

443.

D.

J.

Patmore

and

W.

A.

G.

Graham,

Inorg.

Chem.,

1966, 5, 2222.

and

P.

Woodward,

Chem.

Comm.,

1966,

253.

5035.

F.

Ronati,

8.

Cenini,

D.

Morellj,

and

R.

Ugo,

J.

Chem.

Xoc.

(A),

1966. 1052.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

222

INORGANIC CHEMISTRY

(X

=

Me, H).l75 The details have been given

174

for insertion of fluoro-

olefins between the tin and manganese atoms in Me,Sn-Mn(CO),, briefly

reported last year.

This is in contrast with the results for the corresponding

reactions

of

the compound Me,GeMn(C0),.175

OrganometaUic

Compounds

of

the

Transition

Metals

+Bonded

Organometallic Compounds.-Reaction of dicyclopentadienyl-

zirconium &chloride

176

with triethylaluminium is comidered to give the

bridging group ZP-CH,CH2-ZrIV.

The reaction

77

of

diphenylacetylene

with biscyclopentadienyltitanium dicarbonyl gives the titanium heterocyclic

ring

(1).

The unstable alkyl zirconium methyl complexes Zr(CH,), and Li,Zr(CH,)6

have been observed in the reaction between methyl-lithium and zirconium

tetrachloride.l78 Reduction

of

alkyl halides and olefins with chromous salts

is

considered to involve chromium(m)-ally1 intermediates.179~

l80

The

kinetics of hydrolysis and the kinetics

of

the reaction

of

mercury chloride

with six complex

penta-aquopyridiomethylchromium(m)

ions are re-

ported.lgl The preparation

of

some benzyl-chromium(

m)

complexes,

[CrC&(py),L]

(L

=

benzyl, o-chlorobenzyl, p-chlorobenzyl) has been re-

ported, and the use

of

these as sources of benzyl anions and radicals has

been investigated.ls2 The conversion of o-aryl chromium complexes

of

the

type

R3Cr(THP),

into n-complexes by suitable solvents has been studied;

whereas conversion was possible with the ligands

C,H,-C,H,

and CH,c,H,,

the trimesityl complex failed to rearrange.lB3 The X-ray structure

of

one

of

the first o-bonded arylchromium(

m)

complexes, CI,Cr(THF)#-tolyI, has

been published. The

(3-0

bond

trans

to the p-tolyl group

is

significantly

longer than the other two Cr-0 bonds

(3-21

and

2.04&

respectively) and

this

is

attributed to a

trans

effect of the p-tolyl group.lg4

A

series

of

aryl-

173

N.

Flitcroft,

D.

A.

Harbourne,

I.

Paul,

P.

M.

Tucker, and

F.

G.

A.

Stone,

J.

Chem.

174

D.

J.

Patmore

and

W.

A.

G.

Graham,

Inorg.

Chem.,

1966,

5,

1586;

H.

C.

Clark

175

H.

C.

Clark,

J.

D.

Cotton, and

J.

H.

Tsai,

Inorg.

Chem.,

1966,

5,

1582.

176

H.

Sinn

and

E.

Kolk,

J.

Organometallic Chem.,

1966, 373.

177

K.

Sonogashira and

N.

Hagihara,

Bull.

Chem.

SOC.

Japan,

1966,

39,

1178.

178

H.

J. Berthold and

G.

Groh,

Awgew.

Chem.,

1966,

78,

495.

17n

C.

E.

Castro,

R.

0.

Stephens, and

S.

MojB,

J. Amer.

Chem.

SOC.,

1966,

88,

4964.

180

J.

K.

Kochi

and

P.

E.

Mocadlo,

J. Amer.

Chem.

SOC.,

1966, 88,4094.

181

R.

0.

Coombes and

M.

D.

Johnson,

J.

Chm.

SOC.

(A),

1966, 1805.

182

R.

G.

Coombes and

M.

D.

Johnson,

J.

Chm.

SOC.

(A),

1966,177;

R.

P.

A.

Sneeden,

18s

G.

Stolze,

J. Organometallic

Chem.,

1966,

6,

383;

G.

Stolze and

J.

Hlihle,

ibid.,

lS4

J.

J.

Daly,

R.

P.

A.

Sneeden, and H.

H.

Zeiss,

J. Amer.

Chm.

SOC.,

1966,

88,

SOC.

(A),

1966, 1130.

and

J.

H.

Tsai,

&d.,

p.

1407.

H.

P.

Throndsen,

J.

Organometallic

Chem.,

1966,

6,

542.

p.

645.

4287.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

EOHL AND

LEWIS

:

TRANSITION-METAL

CARBONYLS

223

chromium(m) aryl complexes related to some

of

the allyl derivatives dis-

cussed in the previous Report has been obtained. The complex

Na,[Cr( C,H,),Et20],2Ef,O has been obtained in diethyl ether from phenyl-

sodium and CrCI,, (THF),. With excess

of

phenylsodium the hexaphenyl

complex Na,[Cr(C,H,),,xEt,O]

is

obtained;

it

is

only

stable in excess

of

phenylsodium.185 Reaction

of

the pentaphenyl compound with the

chromium trichloride adduct, CrCl,,(THF), in diethyl ether yields the

complex Na,[ Cr,( C6H,),,3Et,0]. Chromium(

II)

phenyl derivatives may be

obtained by reduction of the corresponding chromium(m) phenyl complexes

with the production of biphenyl. The reduced paramagnetism of these

derivatives

is

associated with the presence of chromium-chromium inter-

action

of

the type observed in chromous acetate.ls6

A

a-bemyl derivative of the composition C,H,( CO),MoCH,C6H5 has been

prepared from the reaction of benzyl chloride with the cyclopentadienyl-

tricarbonylmolybdenum anion.

On irradiation in hexane solution this

is

converted into a n-benzyl derivative C,H&H,MO(C~)~( C,H,) (see below).l8'

The reaction of chloromethyl isocyanate, with the same molybdenum anion,

yields the complex [(CO),C,H,MoCH&CO]

;

with the corresponding iron

anion, [FeC,H,(

CO),]

-,

the compound

(

C,H,),Fe,(

CO),(

CH,NCO)

was

obtained.l88 The preparation of the &st aryl-rhenium complexes has been

given; the complexes formed are [Re(R),(PR,),], [ReR,(PR,),],, and

[ReNR,(PR,),] (R

:

Ph, CH,C,H,; PR,

=

Ph,P or Et,PhP).lsg The X-ray

structure of the iron carbonyl adduct with the Schiff base from p-toluidine

and benzaldehyde has been reported. In [MeC,H,NCH,C,H,]E"e,( CO),, both

o-

and n-bonding between the iron and the arene ring are involved

(2).

With the azobenzene adduct [Fe(CO) ,],PhN=NPh, a different structure is

obtained, with rupture

of

the nitrogen-nitrogen bond and rearrangement

to

form

a

o-semidine skeleton.lS0

The preparation and structure of stable allyl cobaloximes

RCo(D,H,)B

(R

=

alkyl;

D

=

dianion

of

1,2-dioximes;

B

=

base) has been established.

The relationship

of

those systems to vitamin

B,,

derivatives is considered,

and

binuclear cobaloximes containing the unit Co(CH,),Co

(n

=

3,4)

have

lS6

F.

Hein

and

K.

Schmiedeknecht,

J.

Organometallic

Chem.,

1966,

5,

454.

ls6

F.

Hein

and

K.

Schrniedeknecht,

J.

Organometallic

Chem.,

1966,

6,

45.

la7

R.

B.

King

and

A.

Fronzaglia,

J.

Amer.

Cherra.

SOC.,

1966,88, 709.

lgo

P.

E.

Baikie

and

0.

S.

Milk,

Chem.

Com.,

1966, 707.

R.

B.

King

and

M.

B. Bisnette,

Inorg.

Chem.,

1966,

5,

306.

J.

Chatt,

J.

D.

Garforth,

and

G.

A.

Rowe,

J.

Chena.

Soc.

(A),

1966,

1834.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

224

INORGANIC CHEMISTRY

been synthesised.lgl The preparation of an extensive series of alkyl and

aryl derivatives

of

cobalt(m) aetioporphyrin has been reported. The n.m.r.

signals

of

the protons of the alkyl derivatives fall in the range

z

1615.

Crystalline ethyl and p-tolyl derivatives of iron(m) zetioporphyrin have

also

been obtained.192 The stable organo-compounds RCo(BAE) and

RCo(BAE33,O

(BAE

=

bisacetylacetone-ethylenediamine

;

R

=

CH,,

C,H,,

C,H,)

have been formed by the reaction of Grignard reagents or aryl-lithium

with the complexes [Co(BAE)(NH,),]Br or [Co(BAE)PPh,Br].lS3 The

utility of

diethylbisbipyridylcobalt

as a butadiene dimerisation catalyst has

been exp10red.l~~ The reaction of methyl Grignard reagents with the new

complex C,H,CoI,Ph,P leads to the dimethyl derivative.lg5 Rhodium@)

methyl adducts have been obtained by oxidative addition

of

methyl iodide

to

Rh' complexes; with the complex (Ph,P),RhCl the complex

RhIMe(Ph,P),(MeI) was 0btained.1~~ The reaction of methyl iodide (and

bromide) with the

biscarbonylchloro-rhodium

dimer

in

the presence of sodium

cyanide yields the complex K2[MeRh(CN),(H,0)].197 The reaction of

ethylene with the hydride obtained from the action

of

hydrogen chloride gas

on the complex (Ph,P),RhCl in chloroform solution yields the ethyl complex

(PPh,),RhC,H,Cl,

;

with acetylene a vinyl adduct (PPh,),Rh( CH=CH,)CI,

is

obtained.198 The interaction of acrylonitrile and rhodium trichloride-

pyridine yields

a

o-bonded complex (py),RhCI,-CH( CH,)CN, the same

ligand was Qbserved when the hydride (Ph,MeAs),RhHCI, reacted with

acrylonitrile

to

give

(P~~~AS),R~C~,~CH(M~)CN.~~~

Some trimethyl-

iridium

phosphine derivatives Me,Ir(PR,) were obtained

from

the chloro-

phosphine complexes

by

reaction with Grignard reagents

;lg9

a

similar

reaction occurs with tris(dimethy1 sulphide)rhodium(

m)

chloride, to

give

the

binuclear complex (Me,S),Me,Rh,I, which was transformed into the

cyclopentadienyl complex C,H,RhMe,( SMe,)

.

The structures of these com-

plexes are elucidated from the 103Rh-lH coupling constants.200 The pre-

parations

of

the a-bonded nickel complexes R,Ni(bipy)

(R

=

Me,

Et),201s

202

trans-NiXR(PMe,Ph),, and trans-NiR,(PMe,Ph),

(R

=

o-tolyl, mesityl,

naphthyl, pentachlorophenyl, pentafluorophenyl

;

X

5

halogen)

,03

have

been given.

It

was

shown

that the ligand tris-2- (2-biphenylyl) phosphite

lgl

G.

N.

Schrauzer and

R.

J.

Windgassen,

J.

Amer. Chem.

SOC.,

1966,

88,

3738;

G.

N.

Schrauzer and

R.

J.

Windgassen,

Chena.

Ber.,

1966,

99,

602.

lea

D.

A.

Clarke,

R.

Grigg, and

A.

W. Johnson,

Chem. Comrn.,

1966,

208.

lQ3

G.

Costa, G. Mestroni,

G.

Tauzher, and

L.

Stefani,

J.

Organometallic Chem.,

1966,

6,

181.

lQ4

T.

Saito,

Y.

Uchida,

A.

Misono, A. Yamarnoto,

K.

Morifuji, and

S.

Ikeda,

J.

Organometallic

Chem.,

1966,

6,

572.

lQ5

R.

B.

King,

Inorg. Chem.,

1966,

5,

82.

D.

N.

Lawson,

J.

A.

Osborn,

G. Wilkinson,

J.

Chem.

SOC.

(A),

1966, 1733;

M.

C.

Baird,

D.

N.

Lawson,

J.

T. Mague,

J.

A.

Osborn, and

G.

Wilkinson,

Chem.

Comm.,

1966, 129.

1Q7J.

P.

Maher,

Chem.

Comm.,

1966, 785.

lQ*

K.

C.

Dewhurst,

Inorg.

Chem.,

1966,

5,

319.

lQ9

J.

Chatt and

B.

L.

Shaw,

J.

Chem.

SOC.

(A),

1966, 1836.

2oo

H.

P.

Fritz and

K.

E.

Schwarzhans,

J.

Organometallk Chem

.,,.

1966,

5,

283.

201

T.

Saita,

Y.

Ushida, A. Misono,

A.

Yamamoto,

K.

Morifuji, and

S.

I.

Keda,

202

G.

E.

Wilke and

E.

Herrman,

Angew. Chem.,

1966,

78,

591.

203

J.

R.

Moss

and

B.

L. Shaw,

J.

Chem.

SOC.

(A),

1966 1793.

J.

Amer.

Chem.

Xoc.,

1966,

88,

5198.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

KOHL

AND

LEWIS

:

TRANSITION-METAL CARBONYLS

225

stabilises nickel-carbona- bonds

in

the complex

[

(

C6H,-C,H4O),P],Ni( CH,),.

202

A

variety of allyl, aryl, and alkynyl nickel cyclopentadienyl compounds

of the type C,H,Ni(L)(R)

(L

=

phosphine, arsine, stibine) has also been

0btained.20~ Bistritylnickel was obtained by the interaction of bis-( cyclo-

octa-1,3-diene)nickel(O)

with hexaphenylethane,

or

nickel acetylacetone with

hexaphenylethane

in

the presence

of

diethylahminium ethoxide.

The

pure solid compound is not air-sensitive but decomposes

in

argon at

120'0

and reacts with triphenylphosphine to give the

tetrakistriphenylphosphine-

nickel(0) ~omplex,~O~

(Ph,C),Ni

+

4PPh,

+Ni(PPh,),

+

Ph,C--CPh,.

A

novel method for the preparation of ally1 derivatives of pIatinum(lr)

has been observed

;

octene reacts with lithium tetrachloroplatinate(n)

in

the presence

of

formic acid in dimethylformamide to give [octylPt(CO)ClJ,

which with acetylacetone and triphenylphosphine yields [octylPt(CO)(acac)]

and the acyl adduct

[octyl-C0.Pt(Ph3P),C1].206

The nature of

a

series

of

platinum-carbon bonded @-diketone compounds has been investigated, and

the utilisation

of

the unco-orhated carbonyl oxygens

of

these complexes

as potential donor groups el~cidated.~O7 The X-ray structures of some cyclo-

propane complexes

of

platinum have been determined. The complex

C3H,Ptpy2C12 has been found to have a four-membered carbon-platinum

I

Et

--c

H'

lb

ring

system, whilst reaction

of

this complex with carbon tetrachloride

or

chloroform gives a compound having the structure shown

in

(3).

The

bonding between the carbon group and the platinum

is

considered to

be

an

ylide rather than a carbene structure.208 Bromination

of

the a-allyl-

phenyldimethylarsine

(L)

complex

of

platinum, PtBr,(

L)2,

has been shown

to lead to the formation of a platinum-carbon bond with concomitant

rearrangement of one of the allyl arsine derivatives to give an isopropy

grouping.

An

X-ray structure analysis

of

the ethoxy-derivative has been

carried out.209 The n.m.r. spectra of a large number of trimethylplatinum(rv)

H.

Yamazaki, T.

Nishido,

Y.

Hatsumoto,

S.

Sumida, and

M.

Hagihara,

J.

Organo-

metallic

Chem.,

1966,

6,

86.

,05

(3.

Wilke

and

H.

Schott,

Angew.

Chem., 1966, 78, 592.

206

D.

Wright,

Che'Ln. Comm., 1966, 197.

$07

D.

Gibson,

J.

Lewis,

C.

Oldham,

J.

Chm.

SOC.

(A),

1966, 1453;

J.

Lewis

and

208

W.

A.

Bailey, R.

D.

Gillard,

M.

Keeton,

R.

Mason,

D. R.

Russel,

Chem. Comm.,

*O0

M.

A.

Bennett,

G.

J.

Erskine,

J.

Lewis, R.

Mason,

R.

S.

Nyholm,

G.

B.

Robertson,

C.

Oldham,

ibid.,

p.

1456.

1966, 396.

and

A.

D.

C.

Towl,

Chem.

Cmm.,

1966, 395.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

226

INORffANIC CHEMISTRY

(allyl)Pd,

,,

CH

*C02Et

CI

derivatives have been obtained,210 and the structure of the hydroxy-

compound, [Me,PtOH],, determined from n.m.r. and infrared data.211 The

conditions for the preparation

of

almost pure phenylcopper were reported.212

A

carbon-bonded p-diketone adduct of gold@) has been prepared by reaction

of triphenylphosphine gold halides with thallous a~etylacetone.21~

The X-ray structure

of

ethyl zinc iodide indicates that it is a co-ordinated

polymer with iodide bridges.214 The molecularity

of

a series of alkylzinc

derivatives

in

benzene has been determined.215 The

X-ray

structure

of

methyl zinc methoxide shows it to have a tetrameric structure with the zinc

atom at the corners

of

a tetrahedron.216

The search

for

metal carbene complexes has continued during the past

year. The X-ray structure of the

methylmethoxycarbene-phosphine

com-

plex, Me(MeO)C.Cr(CO),(PPh,), has been carried The presence of

a

metal carbene intermediate has been postulated in the reaction

of

tetra-

fluoroboric acid with the compound C,H,Fe( CO)2CH,0Me

as

the complex

[C,H,Fe(CO),CH,]

+BF,-

;

norcarane is formed if the reaction

is

performed

in

the presence of cyclohexene, and cis-but-2-ene is transformed into

cis-l,2-

dimethylpropane.21*

Di-p-dichloro-bis-n-allyldipalladium

(4)

is considered to

react with diazoacetate to give

a

carbene intermediate, as alkenes are con-

verted

into

cyclopropane carboxylic esters.

219

L

RzC=CRz

+

I

>C.H+CO,Et

5

J

R?

L

Dfazomethane reacts with the complex (Ph,P),IrCQCl to give a methylene

insertion reaction, with the formation of (Ph,P),IrCO(CH,Cl). The reactivity

of

the product is explained

in

terms of the conversion into a methylene

carbene intermediate from the chloromethyl group.220

A

series of vinyl-metal complexes has been obtained. The reaction of

diphenylketen with iron pentacarbonyl gives

a

compound whose X-ray

structure establishes the complex as

diphenylvinylideneoctncarbonyldi-

iron.

221

A

new cyclopentadienyl oxy-a-vinyliron group

has

been identified

alo

K.

Kite,

J.

A.

S.

Smith, and

E.

J.

Wilkins,

J.

Chew,.

SOC.

(A),

1966, 1744.

21a

G.

Costa,

A.

Camus,

L.

Gatti, and

N.

Marsich,

J.

Organonzetallic

Chem.,

1966,

ala

D.

Gibson,

B.

F.

0.

Johnson,

J.

Lewis,

and

C.

Oldham,

Chem.

and Ind.,

1966,342.

214

P.

T.

Rloseley and

H.

M.

M.

Sheerer,

Chem. Comm.,

1966, 876.

$16

J.

Boersma

and

J.

G.

Nottes,

Tetrahedron Letters,

1966, 1521;

G.

E.

Coates and

216

H.

M. M.

Shearer and

C.

B.

Spencer,

Chm.

Comm.,

1966, 194.

*17

0.

S.

Mills and

A.

D.

Redhouse,

Chem. Comm.,

1966,

814.

G.

L.

Morgan,

R.

D.

Rennick,

and

C. C.

Soong,

Inorg.

Chm.,

1966,

5,

372.

5,

568.

D.

Ridley,

J.

Chenz.

Soc.

(A),

1966, 1064.

P.

W.

Jolly and

R.

Pettit,

J.

Amer. Chem.

Soc.,

1966,

88,

5044.

R.

I(.

Armstrong,

J.

Org.

Chem.,

1966,

31,

618.

220

F.

D.

Mango and I. Dvoretzky,

J.

Amer. Chm.

SOC.,

1966,

88,

1654.

z21

0.

S.

Mills

and

A.

D.

Redhouse,

Chem.

Comm.,

1966,

444.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

KOHL

AND

LEWIS

:

TRANSITION-METAL

CARBONYLS

227

from the X-ray structure of one

of

the reaction products from the interaction

of iron pentacarbonyl with methylphenylpropiolate

222

(5).

COzMe

co

Ph'

'C02Me

c=c'

The reaction

of

acetylene with the hydride (Ph3P),RhHC1, yields the

vinyl complex (Ph,P),RhCl,( CHCH,).lS6

l-Chloro-2,2-diphenylvinylsilver

has been obtained from the metathesis

of

the lithium compound and silver

chloride.

223

Fluorine-containing a-Carbon

Complexes.-The

19E'

n.m.r. spectra of

m-

and

p-fluorophenylplatium(n)

compounds have been utilised to indicate

the relative

n

and

0

properties

of

other ligands in the molecule.224 The

preparation

of

the compound (C,H,),Zr(C,E",), has been given; the compound

is

chemically less robust than the titanium derivative.225 The comparison

of

the metal-carbon bond lengths obtained by X-ray structure analysis o

the complexes C,H,Mo(CO),X

(X

=

C3F, and

C,H5)

indicates the presence

of

n-bonding in the metal-carbon bond

226

for the fluorine compound. The

reaction

of

pentafluorobenzenethiol with the pentacarbonyl hydrides

cf

manganese and rhenium yields the

pentafluorophenylpentacarbonyl

com-

plexes C,F,M(CO),

(M

=

a,

Re)

;87

pentafluoropyridine and pentafluoro-

benzonitrile react with manganese and rhenium pentacarbonyl anions to

give the 3-substituted tetrafluoropyridine and tetrafluorobenzonitrile penta-

carbonyl adducts, respectively.

227

The reaction

of

lithium pentafluorophenyl

with the cation [C,H,Fe(CO),]+ gives

a

mixture of the pentafluorobenzoyl

complex C,H,Fe( C0),COC6F, and the

0-

bonded pentafluorophenyl com-

pound C,H,Fe

(

CO),-C,F5

;

in contrast, the corresponding triphenylphosphine

cation, [C,H,Fe( CO),PPh,]

f,

reacts to give addition

of

a

pentafluorophenyl

group to the cyclopentadienyl ring with formation

of

a

diene complex,

(C,M,C,F,)Fe(CO)2(YPh3).228

The higher stability

of

metal-carbon o-bonds

in fluoro-complexes

is

emphasised

in

the

reaction

of

hexa>fluorobut-Zyne

with the rhenium peiitacarbonyl amnion, yielding the first allene in which

a

o-bond to a tramition metal occurs, [(F2C=C=C) (CF,)*Re(CO),]

;

a substituted

fluorocyclobuta,iie adduct is also obtained.

229

a-Bonded rhenium peiita-

carbony1 and cyclopentadienyliron dicarbonyl adducts of perfluorobuta-

1,3-

diene have besn reported.229 The interaction

of

fluorinated olefins and

2t2

L.

F.

Dahl,

R.

J.

Doedens,

W.

Hubel,

and

J.

Nielsen,

J.

Amr.

Chenz.

Soc.,

1966,

88,

446.

223

G.

Kobrich,

H.

Frohlich,

and

W.

Drischel,

J.

OrgunometuZZic

Chem.,

1966,

6,

194.

224

E.

W.

Parshall,

J.

Amer. Chem.

SOC.,

1966,

88,

704.

2a5

M.

A.

Chaudhari

and

F.

G.

A.

Stone,

J.

Chem.

SOC.

(A),

1966, 838.

226

M.

R.

Churchill

and

J.

P.

Fennessey,

Chsm.

Comm.,

1966, 695.

227

B.

C.

Booth,

R.

N.

Haszeldine,

and

M.

€3.

Taylor,

J.

Urgunometallic

Chem.,

1966,

228

M.

Green,

W.

Mayne,

and

F.

G.

A.

Stone,

Chem. Comm., 1966,

755.

6,

570.

P.

M.

Treichel

and

R.

L.

Shubkin,

J.

Orgunometallic

Chem.,

1966,

5,

488.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

228

INORGANIC

CHEMISTRY

substituted fluorinated benzene compounds with manganese and rhenium

pentacarbonyl anion and cyclopentadienyl iron dicarbonyl anion leads

to

the formation

of

complexes with metal-carbon ~-bonds.~~O Heptafluoro-

propyl iodide

is

found to react with the compound C,H,Co(CO)PPh, to yield

C,H,COI(C~F,)PP~,.~~~A new tetranuclear nickel cluster, [(CF3),C,],Ni,(C0),,

has been obtained from the interaction

of

hexafluorobut-2yne and nickel

carbonyl

;

the compound

is

formulated as involving hexafluorobut-2-ene

bridges.231 Perftuorovinyl complexes of platinum have been prepared by

reaction of fluoro-olefins

232

and fluoroacetylenes

152

with platinum phos-

phine hydride complexes, whilst addition

of

fluoro-olefins to tetrakistri-

phenylphosphineplatinum(

0)

yields the cyclic o-bonded complexes

(6).

(6)

Reaction

with

perfluoroacetone yields a novel three-membered ring complex

in

which the platinum bonds to both the oxygen and the carbon

of

the per-

fluoroacetone molecule, (Ph3P),Pt(CF3)2C0.233 Addition

of

fluoro-acetylene

complexes to

tetrakistriphenylphosphine

complexes of palladium

234

and

platinum

152

yield the bistriphenylphosphine cyclic a-bonded olefin metal

complexes (Ph,P),M(C,RR)

(M

=

Pd,

R

=

R'

=

CP3;

M

=

Pt,

R'

=

CF,,

R

=

H).

Complexes of bisperfluoroallyl mercuric complexes with a variety

of

oxygen and nitrogen ligands have been described.235

Carbonylation

and

Related

Reactions.-The stereochemistry

of

carbonyl

insertion reactions

of

methylmanganese pentaFarbony1 using phosphines as

the attacking ligands has been studied; a stereospecific reaction to give the

cis-acyl adduct has been observed with the phosphine

P(

OCH,),-CCH3.

236

The presence

of

rotational isomers in the acylpentacarbonyl manganese

system, CXH,COMn(CO),, CHX,COMn(CO),

(X

=

F,

Cl)

has been detected

by infrared measurements over a range

of

temperature.237 The variation

in

the formation of acyl compounds with metal complex has been extended

by a study involving some novel ligand molecules. 2-Chloroethyldimethyl-

amine reacts with the

iron

anion [Fe(CO),(C,H,)]- to give the acyl complex

[Me,NCH,CH,COFeCO(C,H,)I

and the salt

[C5H5Fe(CO),*NMe2CH2CH2Fe(

CO),C,H,]CZ

;

N-l-chloroethylpiperidinereacts

to give C,H1oNCH,CH,Fe( CO),C,H,, and analogous complexes are obtained

with 2-chloromethylpyridine with both the anions [Fe(CO),(C,H,)]- and

a30

M.

I.

Bruce

and

F.

G.

A.

Stone,

J.

Chern.

SOC.

(A),

1966,1837;

M.

I.

Bruce,

P.

W.

231

R.

B.

King,

M.

I.

Bruce,

J.

R.

Philips,

and

F.

G.

A.

Stone,

Inorg.

Chern.,

1966,

z33

M.

Green,

R.

B.

L.

Osborn,

A.

J.

Rest, and

F.

G.

A.

Stone,

Chem. Comm.,

1966,

234

E.

0.

Greaves and

P.

M.

Maitlis,

J.

Organometallic

Chem.,

1966,

6,

104.

zs6

H.

B.

Powell and

J.

J.

Lagowski,

J.

Chern.

SOC.

(A),

1966, 1282.

z36

M.

Green

and

D.

C.

Wood,

J.

Amer. Chem.

SOC.,

1966,88, 4106.

337

F.

Cdderazzo,

K.

Noack,

and

U.

Schaerer,

J.

Organometallic

Chem.,

1966,6, 265.

Jolly,

and

F.

0.

A.

Stone,

ibid.,

p.

1602.

5,

684.

H.

C.

Clark and

W.

S.

Tsang,

Chem.

Comm.,

1966, 123.

602.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

EOHL

AND

LEWIS

:

TRANSITION-METAL

CARBONYLS

229

[W(CO),C,H,]-. With the molybdenum anion [n-C,H,Mo(CO),]-, however,

2-chloropyridine yields an acyl complex, [NC,H,CH,COMo( CO),C5H5].

The manganese pentacarbonyl anion gives

a

cyclic acyl product with

2-chloroethyldimethylamine,

[NMe,CH,CH,COMn( CO),], and with 2-chloro-

methylpyridine [NC,H,CH,COMn(

CO),].

238

Acyl derivatives of the type trans-[MX(COR)(PEt,),]

(M

=

Pd, Pt;

X

=

Cl,

Br,

I,

R

=

Me, Et,

or

Ph) have been obtained

by

the reaction

of

carbon monoxide with the appropriate alkyl

or

aryl c0mplex.23~

Insertion reactions analogous to carbonylation have been found to occur

with sulphur dioxide,

to

yield

Mn(CO)&302R

complexes

(R

=

Me; CH,Ph)

by reaction of the alkyl pentacarbonyl manganese with liquid sulphur

dioxide.

240

A large range

of

cyclopentadienyl iron sulphinatodicarbonyl

complexes

is

obtained by a similar process, and alternative methods

of

pre-

paring these compounds have been illustrated.

241

Decarbonylations

of

a variety of organic acyl and aryl compounds with

the complex (Ph,P),RhCl have been investigated.

242

Olefin-Metal

Complexes.-The mechanism of the isomerisation

of

olefins

by

transition-metal ions has been discussed

in

terms

of

the alkyl

and

ally1

the0ries,24~ and the mechanism of hydrogen migration

in

cycloheptatriene-

molybdenum tricarbonyl complexes has been

Mono-o1efins.-The kinetics and mechanism

of

the hydrolysis

of

the

palladium-ethylene system

to

acetaldelyde have been investigated.245

A

molecular orbital treatment

of

the ultraviolet polarised crystal spectrum

of

Zeise's salt, K[Pt(C,H,)Cl,]H,O, has been reported.246 The proton n.m.r.

spectra of Zeise's salt and related molecules have been used to determine the

orientation

of

the olefin to the plane of the platinum-chlorine system.247

The far-infrared spectra

of

a series of ethylene-platinum complexes have

been observed,2** and a normal co-ordinate analysis

of

the infrared spectra

of

Zeise's salt was carried 0ut.2~9

A

number

of

compounds have been reported

in

which,

in

addition

to

co-ordination of the olefin, bonding of the ligand occurs at other centres.

Iq

the complex

Me,AsC=C(AsMe,)CF,CF,[Fe(

CO),],

one of the iron atoms is

octahedrally co-ordinated to three

CO

groups and the two arsenic atoms with

a metal-metal bond

in

the sixth position; the remaining iron

has

trigonal-

bipyramidal stereochemistry with three carbonyl groups, a metal-metal

11

238

R.

B.

King

and

M.

B.

Bisnette,

Inorg. Chem.,

1966,

5,

293.

23s

G.

Booth and

J.

Chatt,

J.

Ch.

SOC.

(A),

1966, 634.

e40

I?.

A.

Hartman and

A.

Wojcicki,

J.

Amr.

Cham.

Soc.,

1966,

88,

844.

241

J.

P.

Bibler

and

A.

Wojcicki

J.

Amer.

Chem.

SOC.,

1966,

88,

4862.

J.

Tsuji and

K.

Ohno,

J.

Amer.

Chem.

SOC.,

1966,88,3452;

J.

Blum,

Tetrahedron

ars

R.

Cramer,

J.

Am. Chem.

SOC.,

1966,

88,

2272;

R.

Cramer and

R.

V.

Lindsey,

244 W.

R.

Roth and

W.

Grimme,

Tetrahedron

Letters,

1966,

2347.

ap5

R.

Jira,

J.

Sedlmeier,

and

J.

Smidt,

Annakn,

1966,

693,

99.

a47

H.

P.

Fritz,

K.

E.

Schwarzhans,

and

D.

Sellman,

J.

OrganometaUic Chem.,

1966,

24a

H.

P.

Fritz

and

D.

Sellmann,

J.

Organometdic Chem.,

1966,

6,

558.

249

M.

J.

Grogan

and

K.

Nekamoto,

J.

Amer. Chem.

SOC.,

1966,

88,

5454.

Letters,

1966, 1605;

J.

Tsuji

and

K.

Ohno,

ibid.,

p.

4713.

ibid.,

p.

3534.

J.

W.

Moore,

Acta

Chem.

Scad.,

1966,

20,

1154.

8,

551.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

230

INORGANIC CHEMISTRY

bond, and co-ordination to the olefin group of the cyclobutene ring.250

The ligand

2-allylphenyldiphenylphosphine

(AP),

CH,=CH*CH,*C6H4PPh2,

acts as a chelate with an olefin and phosphorus group bonding to give the

compounds

(AP)M(CO),

(M

=

Cr,

Mo,

W),251 whilst in the complex

trans-

2,2'-di-

(di-o-tolylphosphino)stilbenerhodium

chloride, the organic group acts

as a terdentate ligand, bonding by two phosphorus atoms and the oleh

group.252

A

new type of zerovalent metal complex tris(methy1 vinyl ketone)-

tungsten has been reported; co-ordination of both the olefm and the

60

group to give

a

bidentate chelate are postulated.66

The photochemical preparation

of

some new iron tetracarbonyl complexes

of vinyl chloride, styrene, propene, and ethyl vinyl ether

is

reported. The

infrared data imply that the organic groups are co-ordinated through their

olefinic double bond.252 The X-ray structure

of

the fumaric acid-iron

tetracarbonyl complex confirms that co-ordination

of

the acid to the metal

occurs through the double bond.

253

A series of gold chloride olefin complexes

with a large range

of

cyclic mono- and di-olefins has been reported.254 The

X-ray structures of the

following

silver(1) olefin adducts have been carried

out

:

the norbornadiene adduct C,H,,2AgN0,,255 the bulvalene complex

CloHlo,3AgBF4,256 and the complex C6H,-Ag*AlC1,.257 The structure of the

copper complex C6H,CdC1, is analogous to that of the benzene silver

complex.

25,

Polyene

Systems.-The study

of

the proton n.m.r. spectra over a tempera-

ture range

for

a series of cyclo-octatetraene metal carbonyls, C,H,M(CO),

(M

=

Cr,

Mo

,

Pe), together with

1,3,5,7-tetramethylcyclo-octafefraene-

molybdenum tricarbonyl and an extensive range of substituted cyclo-octa-

tetraeneiron tricarbonyl adducts, indicates the presence

of

valence tautomer-

isation in these systems. The bonding

of

the complexes has been interpreted

in

favour

of

both 1,3-diene and 1,5-diene co-ordination

of

the ring system

to the metals.259

For

the tungsten analogue,

c,H,w(Co),,

the n.m.r. spectra

at room temperature show the anticipated four sets

of

hydrogen signals.66

From the n.m.r. spectrum, valency tautomerism has also been suggested to

be present

in

cyclo-octatetraenecobalt

cyclopentadienyl.260

In

both the

cyclobutadiene and butadiene iron tricarbonyls, carbon-

13

and proton n.m.r.

spectra have been interpreted as indicating that the carbon atoms involve

s60

F.

W.

B.

Einstein,

W.

R.

Cullen, and

J.

Trotter,

J.

Amer. Chern.

Soc.,

1966,

88,

'ti1

I;.

V.

Interraate,

M.

A.

Bennett, and R.

S.

Nyholm,

Inorg.

Chem.,

1966,

5,

2212.

M.

A. Bennett,

R.

Bramley, and

P.

A.

Longstaff,

Chm. Comm.,

1966,806;

E.

K.

P.

Corrandi,

C.

Pedone, and

A.

Sirigu,

Chem.

Cmn.,

1966, 341.

254

R.

Huttel,

H.

Reinheimer, and

H.

Dietl,

Chm.

Ber.,

1966,

99,

462;

R.

Huttel

256

N.

C.

Baenziger,

H.

L.

Haight,

R.

Alexander, and

J.

R. Doyle,

Inorg.

Chem.,

266

M.

Gary Newton and

I.

C.

Paul,

J.

Amer. Chem.

SOC.,

1966, 88, 3161.

257

R.

W. Turner and

E.

L.

Amma,

J.

Aw. Chem.

SOC.,

1966,88, 3243.

2s8

R. W.

Turner

and

E.

L.

Amma,

J.

Aw.

Chem.

SOC..

1!366,88, 1877.

259

C.

E.

Keller, B.

A.

Shoulders and R.

Pettit,

J.

Amer. Chem.

Soc.,

1966,

88,

4760;

C.

G.

Kreiter,

A.

Maasbol,

E.

A.

L.

Anet,

H.

0.

Kaesz, and

S.

Winstein,

ibid.,

p.

3444;

F.

A.

Cotton,

J.

W.

Faller, and

A.

MUSCO,

ibid.,

p.

4506;

F.

A.

Cotton,

A.

Davison, and

6670.

von

Gustorf,

M.

C.

Henry, and

C.

Di

Pietro,

2.

Nalurforsch., 1966,

21b,

42.

and

H.

Reinheher,

ibid.,

p.

2778.

1966,

5,

1399.

.W.

Faller,

ibid.,

p.

4507.

260

S.

Otsuka and

A.

Nakamura,

Inorg. Chem.,

1966,

5,

2059.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

KOHL

AND

LEWIS:

TRANSITION-METAL

CARBONYLS

231

essentially sp2-hybridisa.tion, and are consistent with bonding

of

the dienes

to the metal in a similar manner to the ferrocene system.261

It

has been found possible to add

1

mol.

of

carbon monoxide to the

complexes C,H,Mo(CO), and

(cyclo-octa-l,3,5-triene)Mo(CO),

to yield

the tetracarbonyl complexes. The n.m.r. proton spectra indicate that

in the resultant complex the ligands are co-ordinated as 1,5-cyclo-octa-

tetraene and 1,5-cyclo-octatriene adducts.26s

The reaction of triphenylphosphine with a series of dieneiron tricarbonyl

complexes to yield some triphenylphosphineiron dicarbonyl diene com-

plexes

263

has been studied. Vitamin

A

aldehyde reacts with iron penta-

carbonyl to give a diene iron tricarbonyl complex. The X-ray structure

of

this compound has been determined.264

A

number

of

/?-ionone iron tri-

carbonyl compounds have been prepared, and their properties reported.265

Butadiene reacts with ruthenium trichloride

in

2-methoxyethanol to

give

dichloro(deca-2,6,10-triene-1,12-diyl)ruthenium(1v).~~~

The complexes

[Ru(CO)CI,(diene)], (diene

=

cyclo-octa- 1,5-diene and norbornadiene) have

been ~repared.~67 Reaction of titanium tetrakisbutoxide with cyclo-octa-

tetraene in the presence of triethylaluminium produces bis( cyclo-octa-

tetraene)titanium and the dimer Ti,(COT),

268

(7)

;

the crystal structure

of

the dimer has been determined; a series

of

new n-complexes

of

iron(0) and

ruthenium(0) with seven- and eight-membered cyclic olefins have been pre-

pared, and the n.m.r. spectra of these complexes assigned.,'*

The

use

of

the intermediates [(olefin),RhCI], (olefin

=

cyclo-octene,

cycloheptene, and norbornene) for the preparation

of

a series

of

diolefh

compounds, [(dioleh),RhCl], has been exploited

;

271

a similar series

of

reactions has been established

for

iridium.,'

The rhodium carbonyl chloride

her, [Rh(CO),Cl],, reacts with cyclohexa-1,3-diene and 2,3-dimethyl-

butadiene to give the adduct [Rh(CO),Cl],diene.

It

is suggested that the

rslH.

G.

Pmton and

J.

C. Davis,

J.

Amer. Chem.

SOC.,

1966,

88,

1585;

H.

L.

Retcofsky,

E.

W.

Franke1;and

H.

S.

Gutowsky,

ibid.,

p.

2711.

a62

S.

Winstein,

J.

Amer. Chem.

SOC.,

1966,

88,

1319.

a63

F.

M.

Chaudhari and

P.

L.

Pauson,

J.

Orgamtallic

Chem.,

1966,5, 73.

864

A.

J.

Birch,

H.

Fitton, R. Mason,

G.

B.

Robertson,

and

J.

E.

Stangroom,

Chem.

886

M.

Cais and

N.

Maoz,

J.

Organometallic Chem.,

1966,

5,

370.

28s

J.

K.

Nicholson and

B.

L.

Shaw,

J.

Chem.

SOC.

(A),

1966, 807.

267

S.

D.

Robinson and

C.

Wilkinson,

J.

Chem.

SOC.

(A),

1966, 300.

268

H.

Breil

and

G.

Wilke,

Angew. Chem.,

1966,

78,

942.

*70

J.

Miiller

and

E.

0.

Fischer,

J.

Organometallic Chem.,

1966,

5,

275.

271

L.

Porri and

A.

Lionetti,

J.

Organometallic Chem.,

1966,

6,

422;

G.

Winkhaus

272

G.

Winkhaus and

H.

Singer,

Chem.

Bm.,

1966,

99,

3610.

Cornm.,

1966, 613.

H.

Dietrich and

H.

Dierks,

Angew.

Chem.,

1966,

78,

943.

and

H.

Singer,

Chem.

Ber.,

1966, 99, 3602.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

232

INORGANIC

CHEMISTRY

diene acts as an additional bridging ligand across the rhodium atoms

of

the carbonyl chloride dimer.,V3 The structure

of

cyclo-octenylnickel(n)

acetylacetone has been determh~ed,~v~ and also that

of

the related platinum

complex

methoxydicyclopentadienechloroplatinum

dimer.275 In both com-

plexes the ligand co-ordinates through both a

n-

bonded metal-oleh

and

a

o-metal-carbon bond. The reactivity

of

diene-palladium and

-platinum complexes towards nucleophilic attack, with the formation

of

compounds typified by the last two structures, has been studied with

acetylacetonate ani0ns~7~ and methoxide ions.277,

,7*

The n.m.r. spectra

of

a series

of

methoxy-derivatives has been used to determine the stereo-

chemistry

of

these products.

278

The carbonylation of cyclo-octa- 1,5-diene

to ethyl

cyclo-octene-4-carbonylate

has been accomplished using the palla-

dium-cyclo-octa-l,5-diene

chloride complex.

279

Buta- 1,3-diene and cyclo-

octa-l,3-dienepalladium dichloride complexes have been obtained by

ligand exchange with

bisbenzonitrilepalladium

dichloride

or

the corres-

ponding pentene complex. The diene complexes are dimers, [(diene)PdCl],,

and are considered to bond through

only

one olefin group. The butadiene

compound isomerises at room temperature to a mallyl compound.

280

The use

of

cyclobutadieneiron tricarbonyl as an intermediate in organic

chemistry

for

the production

of

cyclobutadiene has been illustrated.281 The

reaction of

chloromethylcyclobutadieneiron

tricarbonyl with antimony

pentachloride abstracts the chloride to give

cyclobutadienemethyleneiron

tricarbonyl cations.282 Tetraphenylbutatriene reacts with iron ennea-

carbonyl to give two complexes corresponding to the addition

of

Fe(CO),

and Fe,(CO), units to the ligand;

2B3

the structure

of

the Fe(CO),L adduct

shows that the iron is co-ordinated to the central carbon double bond

284

(8).

A&l

Complexes.-The isomerisation

of

labelled olefins by

iron

and cobalt

carbonyls has been interpreted in favour

of

an ally1 intermediate.285 The

G.

Winkhaus and

H.

Singer,

Ch.

Ber.,

1966,

99,

3593.

274

0.

S.

Mills and

E.

F. Paulus,

Chem.

Comm.,

1966, 738.

a15

W.

A.

Whitta,

H.

M.

Powell, and

L.

M.

Venanzi,

Chem.

Comm.,

1966, 310.

276

B.

F.

G.

Johnson, J. Lewis,

and

M.

S.

Subramaniam,

Chm.

Comm.,

1966, 117.

277

R. G.

Schultz,

J.

Organmetallic Chem.,

1966,

6,

435.

278

J.

K.

Stille and

R.

A.

Morgan,

J.

Amer.

Chem.

SOC.,

1966,

88,

6135.

278

J. Tsuji,

S.

Hosaka, J. Kiji, and

T.

Susuki,

Bull.

Chem.

SOC.

Japan,

1966,39,141.

280

M.

Donati and F. Conti,

Tetrahedron

Letters,

in the

press.

281

J.

C.

Barborak,

L.

Watts, and

R.

Pettit,

J.

Amer.

Chem.

SOC.,

1966,

88,

1328.

283

K.

K. Joshi,

J.

Chem.

SOC.

(A),

1966, 598, 594.

as4

D.

Bright and

0.

S.

Mills,

CM.

Comm.,

1966, 211.

485

B.

Fell, P.

Krings,

and F.

Asinger,

Chm.

Bw.,

1966,

99,

3688.

J.

D.

Fitzpatrick,

L.

Watts, and

R.

Pettit,

Tetrahedron

Letters,

1966, 1299.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

KOHL

AND

LEWIS

:

TRANSITION-METAL

CARBONYLS

233

bonding of n-ally1 complexes to transition metals has been discussed

with

particular reference

to

the stereochemistry of n-allylpalladium chloride and

acetate.286 The detailed structure of acetylacetonate cyclo-octa-2,4-dienyl-

palladium

is

reported;

287

a co-ordinated n-aUyl and free olefin group within

the same organic ring has been established from the X-ray structural analysis

of the binuclear azulene complex Cl,H8Pe2(C0),.288 One of the products

of the reaction

of

cyclo-octatetraene (COT) with

iron

enneacarbonyl,

(COT)Fe,(CO),, has been shown to involve two symmetrically placed ally1

groups, one each bonding

to

an iron atom with the two remaining carbons

of

the ring bonding through two three-centre bonds

to

the two

irons

and

a

bridging carbonyl group.

A

rapid valence tautomerism with rotation of the

iron groups around the ring

is

postulated

289

in order to explain the n.m.r.

rtpectra. The structure

of

perfluorocyclopentadienedicobalt

heptacarbonyl

has shown the presence of

a

Co(CO), fragment a-bonded to the cyclo-

pentadiene ring and a

Co(CO),

group bonded via a n-ally1 system to the

ring.

The variation

in

the proton n.m.r. spectra over a temperature range of a

number

of

metal-ally1 compounds have been studied and have been inter-

preted on the basis of the presence

of

n-a-ally1 equilibria and rotation of the

CH, groups of the n-ally1 system; various allyl complexes of zirconium,291

rhodium,292 and palladium

203

have been studied, and the n.m.r. spectra

utilised to determine the kinetics of the reaction of the complex (C4H,PdC1),

with The a-n-character of the allyl bond

in

the complex chloro-

(triphenylphosphine)(methylallyl)palladium(n),

discussed

in

last year's

Report, has been substantiated by the X-ray structure of the compound.295

However, the importance of viewing

this

as a n-ally1 derivative rather than

a mixed n-olefin and a-carbon bonded species

has

been emphasi~ed.~~~~

294

A

novel n-ally1 system was identified

in

(n-benzy1)molybdenum cyclopenta-

dienyl tricarbonyl in which two of the carbons

of

the benzene ring and the

methylene carbon comprise the co-ordinated n-ally1 group.

In

order to

interpret the n.m.r. proton spectra

of

this compound it

is

postulated that

either the mbenzyl group may rotate about the two-fold axis of the benzyl

ring or that an equilibrium between

n-

and a-structures occurs.192

A

new synthesis of allylbis( cyclopentadienyl) titanium(

m)

derivatives

has been reported.

296

The chemistry of

a

a-allylmolybdenum(n) complex

has been extended. One obtains a series of mononuclear allyl derivatives

286

S.

F.

A.

Kettle and

R.

Mason,

J.

Organometallic

Chem.,

1966,

5,

573.

288

M.

R.

Churchill,

Chem.

Comm.,

1966, 450.

288

E.

B. Fleischer,

A.

L.

Stone,

R.

B.

K.

Dewar,

J.

D.

Wright,

C.

E.

Keller,

and

291

J.

K.

Becconsdl and

S.

O'Brien,

Chem. Comm.,

1966,

302.

2g2

H.

C.

Volger

and

K.

Vrieze,

J.

OrganometaZZic

Chmn.,

1966, 297;

J.

K.

Becconsall

and

S.

O'Brien,

Chem.

Comm.,

1966,

720.

293

G.

L.

Statton and

K.

C. Ramey,

J.

Arner. Chem.

Soc.,

1966,

88,

1327;

K.

C.

Ramy

and

G.

L.

Statton,

ibid.,

p.

4387;

K.

Vrieze,

C.

Maclean,

P.

Cossee,

and

C.

W.

Hilbers,

Rec.

Trav.

chim.,

1966,

85,

1077.

2Q4

K.

Vrieze,

P.

Cossee,

C.

MacLean,

and

C.

W.

Hilbers,

J.

Organometallic

Chena.,

1966,

6,

672.

2Q5

R. Mason and

D.

R.

Russel,

Chem.

Cmm.,

1966, 26.

2*6

If.

A.

Martin

and

L.

Jellinek,

J.

Organometallic

Ch.,

1966,

6,

293.

M.

R.

Churchill,

Inorg. Chem.,

1966,

5,

1608.

R. Pettit,

J.

Amer.

Chem.

Soc.,

1966,

88,

3158.

P.

B.

Hitchcock and

R.

Mason,

Chem.

Comm.,

1966, 503.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

234

INORGANIC CHEMISTRY

by splitting the bridge of the salts

of

tri-~-chlorobis-(2-methyl-n-allyl-

dicarbonylmolybdenum) anion.

297

The preparation

of

three acetyl- or

benzoyl-allylmanganese tetracarbonyl derivatives by interaction of methyl-

or

phenyl-manganese pentacarbonyl with butadiene has been de~cribed,~Qa

and the mechanism

of

this reaction in~estigated.2~~ The reaction of allene

with tri-iron dodecacarbonyl and cobalt octacarbonyl has been reported.

A

rapid valence tautomerism between a 2,2'-bi-n-allylene hexacarbonyl di-iron

structure and

a

butadiene structure

is

deduced from the proton n.m.r.

spectra.300 Trimethylenemethane has been stabilised as a ligand with an

iron tricarbonyl fragment by reaction

of

iron enneacarbonyl with

1

,l-dichloro-

methylethylene, CK2=C(CH2C1), to give

[

(CH,),C]Fe(CO),.

301

A

series

of

0-

and n-ally1 complexes has been isolated from the reaction

of

triphenylphosphinerhodium

chloride with allyl chloride

in

solution.302

Tris-n-allylrhodium has been prepared by reaction of the (bis-n-allylrhodium

chloride) her, [(C,H?),RhCl],, with allylmagnesium chloride. The n.m.r.

spectra indicate that each n-ally1 group

is

symmetrically bonded but that

they are not stereochemically eq~ivalent.~~~~

302

The preparation of allyl-

palladium chloride from chloropalladite and allyl chloride in the presence of

carbon monoxide

is

considered to occur through an oxidative hydrolysis.

This concept has been developed to prepare a number of rhodium allyl

comple~es.~0~

A

series

of

n-ally1 and alkyl nickel phosphine compounds has

been reported

;

304

the preparation of

1,4,7-trimethylenecyclononane

from

1

,I-bischloromethylethylene,

(ClCH,),CCH,, and nickel carbonyl is con-

sidered to occur through a n-ally1 complex.3o5 With iron carbonyl a stable

allyl intermediate is obtained (see above).

The preparation of allylpalladium(n) anions,

[

(n-allyl)PdX,]

-

(X

=

halo-

geIi), is described; they are obtained by reaction

of

excess of halide and the

corresponding n-ally1 halogen dimem306 The reaction of allene

with

chloro-

palladate

(

11)

yields

(

p-

3

-

chloropr

o

p

-

1

-en- 2

-

y

1)

allyl and

2

-

chlor opr

o

p

-

2

-

enyl

palladium complexes.307

Csclopen

tadiene

Complexes

.-T

he analogy between met al-carb orane

derivatives and cyclopentadienyl compounds is emphasised by the X-ray

structure determination

308

of

the anion,

[

(B,C,H,,)Re(CO),], which has the

structure previously proposed.309 The complexes of carboranes with palla-

dium(n) have been established with the preparation

of

the tetraphenylcyclo-

2Q7

H.

D.

Murdoch and

R.

Henzi,

J.

Organometallic

Chem.,

1966,

5,

552.

298

W.

D.

Bannister,

M.

Green, and

R.

N.

Haszeldine,

J.

Chem.

SOC.

(A),

1966, 194.

29s

M.

Green and

R.

I.

Hancock,

Chem. Comm.,

1966, 572.

300

A.

Nakamura,

Bull.

Chem.

SOC.

Japan,

1966,

39,

543.

aol

G.

F.

Emerson,

K.

Ehrlich,

W.

P.

Giering, and P.

C.

Lauterbur,

J.

Amer. Chem.

308

J.

Powell and

B.

L.

Shaw,

Chern.

Comm.,

1966, 323.

J.

Powell and

B.

L.

Shaw,

Chem.

Comm.,

1966,

236;

J.

K.

Nicholson,

J.

Powell,

SOC.,

1966,

88,

3172.

and

B.

L.

Sha,w,

ibid.,

p.

174.

804

B. Bogdanovic,

H.

Bonnemann, and

G.

Wilko,

Angezu.

Chm.,

1966,

78,

591.

805

E.

J.

Corey

and

H.

F.

Semmelhack,

Tetrahedron

Letters,

1966, 6237.

306

R.

J.

Goodfollow and L.

M.

Venanzi,

J.

Chem.

Xoc.

(A),

1966,

784.

807

M.

S.

Lunin.

J.

Powell. and

B.

L.

Shaw,

J.

Chem.

SOC.

(A),

1966, 1687;

B.

L.

..

Shrtw,

ibid.,

p.

f6S8.

308

A.

Zalkin

and

T.

E.

Hopkins,

Inorg.

Chem.,

1966,

5,

1189.

M.

F.

Hawthorne and

T.

P.

Andrews,

J.

Amer. Chem.

SOC.,

1965,

87,

2496.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

KOHL

AND

LEWIS

:

TRANSITION-METAL

CARBONYLS

235

butadiene compounds

[n-(

Ph4C4)Pd(n-BgC2H,,)] and

[z~-(P~*CJP~(~-B~C,H,(CH~),)].~~~

The electron diffraction pattern

of

ferrocene

in

the vapour phase indicates

D,,,

symmetry for the equilibrium conformation; the CH bonds are bent

away from the plane

of

the

C5

ring by

5"

towards the metal.311 The equiva-

lence of the protons of the a-bonded cyclopentadiene group in the n.m.r.

spectrum

of

the compound (C,H,)Fe(CO),( C5H5) has been investigated by

measuring the spectra over a temperature range and by the determination

of the X-ray structure. The data are interpreted

in

terms

of

an intra-

molecular reorientation process.312 The mass spectra

of

some cyclopenta-

dienyl-metal derivatives

3l3

have been obtained, and the nature

of

the

t

etr ac

y

anoe

t

h ylene adduc

ts

of

ferrocene and co balo cene elucidated

.

A

new preparation of

biscyclopentadienyltitanium(n)

has confirmed the

diamagnetism

of

the c0mplex.3~5 Titanium and zirconium cyclopentadiene

alkylphosphide complexes, [C,H,MPR,],

(M

=

Ti, Zr;

R

=

C2H5

or

n-C41Pg)

have been synthesised,"16 and

tetrakiscyclopentadienylzirconium

was re-

in~estigated.3~7 Diphenylketen complexes have been obtained by reaction

of the keten with

biscyclopentadienylvanadium

and with biscyclopentadienyl

titanium dicarbonyl, respectively, to give [C5H5M(Ph2C=C=O)]

(M

=

Ti,

V).

The keten reacts with the metal through the olefin and oxygen groups

of

the diphenylketen.3'8 The interaction

of

the cyclopentadienyl carbonyls

of

iron and vanadium with sulphur yields319 the polymeric complexes

[

(

C,H5),V2S5] and [C5H5FeS],, and whereas cyclohexene sulphide reacts

with the cyclopentadienyl' carbonyl

of

vanadium

319

to give the same

polymeric vanadium product, the complex

[

(

C5R5)MoS2C,H11],

is

obtained

from [C,H,MO(CO),],.~~~~

320

The X-ray structure

of

the iron adduct has

been

321

The complex C,H,V(acetate),

is

considered to be

a

dimer in the solid, and the magnetic moment

(p

=

1.49

B.M.)

is indicative

of interaction between the metal ions.322

A

series of maleonitrile dithiolate

complexes

of

some cyclopentadienyl complexes of titanium, molybdenum,

tungsten, iron, and cobalt has been 0bserved;~~3

a

related cobalt adduct,

C5H5Co [S,C,

(

CF,),],

324

has been obtained with

(trifluoromethy1)dithione.

310

P.

A.

Wegner and

M.

F.

Hawthorne,

Chm.

Comm.,

1966, 861.

311

R.

K.

Bohn and

A.

Haaland,

J. Organometallic

Ckem.,

1966,

5,

470.

312

M.

J.

Bennett,

F.

A.

Cotton,

A.

Davison,

J.

W.

Faller,

S.

J.

Lippard, and

S.

M.

313

F.

J.

Preston and

R.

I.

Reed,

Chent.

Comm., 1966,

51;

E.

Schumacher and

R.

314

R.

L.

Brandon,

J.

H.

Osiecki, and

A.

Ottenborg,

J.

Orgunometallic

Cilem.,

1966,

315

G.

W.

Watt, L.

J.

Baye, and

F.

0.

Drammond,

J.

Amer.

Chent.

SOC., 1966,88,1138.

316

K.

Issleib and H. Hackert,

2.

Naturforsch., 1966,

21b,

519.

317

E.

31. Brainina,

M.

Rh.

Minacheva, and R.

Kh.

Freidlina,

Bull.

Acad.

Sci.,

slsP.

Hong,

K. K.

Sonogashira,

and

N.

Hagiham,

Bull.

Chem.

SOC. Japan, 1966,

s19

R.

A.

Schunn,

C.

J.

Fritchie, and

C.

T.

Prewitt,

Inorg.

Chem.,

1966,

5,

892.

320

P.

M.

Treichel and

G.

R.

TVillces,

Inorg.

Chem., 1966,

5,

1182.

321

C.

H. Wei,

G.

R.

Wilkes,

P.

M.

Treichel, and

L.

F.

Dahl,

Imorg. Chem., 1966,

322

R.

B.

King,

Inorg.

Ch8?n.,

1966,

5,

2231.

s2s

J.

Locket and

J.

A.

McCleverty,

Inorg.

Chem., 1966,

5,

1157.

a24

H.

W.

Baird and B.

M.

White,

J.

Amer.

Chcwt.

SOC.,

1966,

88,

4744.

Morehouse,

J.

Anier.

Chern.

SOC.,

1965,

88,

4371.

Taubenest,

Helv.

C'lzim.

Actn,

1966,

49,

1447.

31,

1214.

U.S.S.R.,

1965, 1839.

39,

1821.

5,

900.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

236

INORGANIC

CHEMISTRY

An

extensive group of arylazo-derivatives

of

molybdenum cyclopentadienyl

carbonyl have been prepared, RN,Mo(CO)~(C,H,).~~~ The product

of

the

reaction of

tetraphenylcyclopentadienone

with triphenyltin manganese

pentacarbonyl has been reformulated as

(tripheny1stannoxy)taphenyl

cyclopentadienylmanganese

tricarbonyl.326

The

preparation

of

benzene

cyclopentadienyl manganese

(

I)

and a related series

of

biphenyl dimeric

species has been described.327,

328

Tropylium derivatives have been obtained

from the Friedel-Crafts acetylation

of

the chromium and manganese cyclo-

pentadienebenzene complexes.328 The compounds C,H,Mo(CO),X, (X

=

C1,

Br,

I)

have been obtained by direct halogenation of the cyclopentadienyl-

molybdenum tricarbonyl ~Iimer,~,~ and the reaction of the cyclopentadienyl

carbonyl chlorides

of

iron and tungsten with unidentate nitrogen and phos-

phorus ligands rep0rted.3~0

The electronic

and structural similarities

of

cyclopentadienyl-carbonyls

and pure carbonyls have been emphasised

in

the

preparation of the complexes [C,H,Fe(

C0)l4

and [C,H,Co(CO)],, and com-

parison with the carbonyls [Co(CO),], and Ru,(

CO),,,

respectively.331

mCyclopentadieneiron tricarbonyl, (C,H,)Fe( CO),, has been obtained

from

cyclopentadiene and iron enneacarbonyl

;

the compound decomposes at

140"

to give the cyclopentadienyliron dicarbonyl dimer.332

Some new

methods for the preparation of alkoxycarbonyl cyclopentadienyl complexes

of

iron, manganese, and molybdenum have been de~eloped.~33 The carbon

monoxide insertion reaction

of

the compound C,H,Fe( CO),CH3, to give

C,H,Fe(CO)(COCH,)L, has been studied with a variety

of

phosphines

(L),334,

335

and the ions [C,H,I?e(CO),L]f are obtained by reaction of the

phosphines with the complexes C,H,Fe(CO),X (X

=

C1,

Br,

I).335

Stable

monomeric alkyl and aryl mercaptide complexes, C,H,Fe(

CO),SR,

have

been isolated

;

the controlled transformation into pairs of isomeric binuclear

complexes

[

(RS)Fe(

CO)C,H,],

has been reported.336 Some alkyl and aryl

trithiocarbonates

of

iron, [C,H,Fe(CO),CS,R] (R

=

CH,, C,H,,

c6H,),

have

been obtained; these lose carbon monoxide in ultraviolet light to yield the

chelated monocarbonyls, [C,H,Fe( CO)CS3R].337 The preparation

of

the

fist trifluorophosphine cyclopentadienyl cobalt complex has been reported,

C,H,CO(PP,),.~~~ The structure of the trimer, [C,H,Rh(CO)],, indicates

a triangular array

of

rhodium atoms with bridging carbonyl groups and a

cyclopentadienyl group associated with each rhodium atom.

339

Dicyclo-

335

R.

B.

King and

H.

B.

Bisnette,

Inorg. Chem.,

1966,

5,

300.

326

R.

D. Gorsich,

J.

Organometallic Chem.,

1966,

5,

105.

327

R. G. Denning and

R.

A.

D.

Wentworth,

J.

Amer. Chem.

SOC.,

1966, 88,4619.

328

E.

0.

Fischer and

S.

Breitschaft,

Chem. Ber.,

1966,

99,

2213.

329

R.

J.

Haines,

R.

S.

Nyholm,

and

M.

H.

B.

Stiddard,

J.

Chem.

SOC.

(A),

1966,

1606.

330

E.

0.

Fischer and

E.

Moser,

J.

Organometallic Chem.,

1966,

5,

63.

331

R.

B. King,

Inorg. Chem.,

1966,

5,

2227.

332

R.

K.

Kochhar and R. Pettit,

J.

OrganometaZZic Chem.,

1966,

6,

272.

533

R.

B.

King,

M.

B.

Bisnette, and

A.

Fronzaglia,

J.

Organometallic Chem.,

1966,

334

J.

P.

Bibler and A. Wojcicki,

Inorg. Chem.,

1966,

5,

889.

335

P.

M.

Treichel,

R.

L.

Shubkin,

K.

W. Barnett,

and

D. Reichard,

Inorg. Chem.,

336

M.

Ahmad, R. Bruce, and

G.

R.

Knox,

J.

Organometallic Chem.,

1966,

6,

1.

337

R.

Bruce and

0.

R.

Knox,

J.

Organomctallic Chem.,

1966,

6,

67.

338

Th.

I<ruck,

W,

Hieber, and W. Lang,

Angew. Chem.,

1966,

78,

208.

539

0.

S.

Mills and

E.

F.

Paulus,

Chem. Comm.,

1966, 815.

5,

391.

1966,

5,

1177.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

KOHL

AND

LEWIS

:

TRANSITION-METAL

CARBONYLS

237

pentadienylrhodium(n), and -iridum(n) have been shown to be paramagnetic

monomers at liquid-nitrogen temperature and

in

the gas phase, but to be

diamagnetic dimers at room temperature.340 Base adducts of tricyclo-

pentadienyl complexes

of

a series

of

lanthanide elements

of

the form

(C,H,),M,L

(M

=

Y,

Nd, Tb, Ho, Yb, L

=

cyclohexyl isonitrile;

M

=

Yb,

L

=

PPh,, OC4H,,

NH,)

have been 0btained.~~1 The preparation

of

tri-

cyclopentadienyleuropium

342

and

dicyclopentadienylytterbium

343

has been

given.343 The syntheses

of

the transuranic cyclopentadienyl compounds

(C,H,),NpC1344 and

Am(

C5H5),345

have also been reported.

Metal-Arene

Complexes.-The low-temperature studies

of

the X-ray

structures

of

dibenzenechromium favour the symmetry

D,,

for the mole-

cule.346 The e.s.r. spectrum

of

the ion [(HMB),Fe]+ (HMB

=

hexamethyl-

benzene) suggests that the two rings are oblique to each 0ther.~47 The

X-ray structures

of

(HMB)Cr(

CO),

and (C6H,)Cr(

CO),

indicate

a

staggered

configuration

of

the rings to the carbon triangle of the carbonyl groups,

whereas

in

the anisole derivative an eclipsed configuration is observed

;

in

con-

junction with these results, and from the structure

of

the (o-toIuidine)Cr(CO),

complex, it

is

concluded that these effects are related to electronic rather than

steric factors.348 The X-ray structure

349

of

1,6-methanocyclodecapentane-

chromium tricarbonyl prepared recently

350

has been reported, and the

high-field shift of the methylene group is

shown

not

to

be associated with

direct metal interaction. The temperature dependence of the proton n.m.r.

spectra of

isopropylbenzenechromium

tricarbonyl is associated with restricted

rotation of the arene nucleus.

351

The X-ray structure

of

the charge-transfer

complex

of

(aniso1e)chromium tricarbonyl with 1,3,5-trinitrobenzene has

been 0btained.~5~

The reaction

of

benzene and methyl-substituted benzene tetracarbonyl

vanadium cations, [(arene)V(CO)4]+, with borohydride

to

give the z-cyclo-

hexadienyl derivatives has been reported. The n.m.r. and infrared spectra

in the region

2770-2820

cm.-l are assigned to the methylene group and not

metal-hydrogen interaction.

353

The preparation of some cyclopentadienyl-

chromium tropylium cations have been rep0rted,~54 and the photochemical

340

E.

0.

Fischer and

H.

Wawersik,

J.

Organometallic

Chem.,

1966,

5,

559.

341

E.

0.

Fischer and

H.

Fischer,

J.

Organometallic

Ch.,

1966,

6,

141.

342

M.

Tsutsui,

T.

Takino,

and

D.

Lorenz,

2.

Naturforsch.,

1966,

216,

1.

343

F. Calderazzo,

R.

Pappalardo, and

S.

Losi,

J.

Inorg.

Nuclear

Chem.,

1966,

28,

344

E.

0.

Fischer,

P.

Laubereau, F. Baumgartner, and B. Kanellakopulos,

J.

Organo-

345

F.

Baumgartner,

E.

0.

Fischer, B. Kanellakopulos, and

P.

Laubereau,

Angew.

346

E.

Keulen and

F.

Jellinek,

J.

Organometallic

Chem.,

1966,

5,

490.

347

H.

Brintzinger,

E.

Palmes, and R.

H.

Sands,

J.

Am.

Chem.

SOC.,

1966,

88,

623.

348

0.

C.

Carter,

A.

T.

McPhail, and

G.

A.

Sim,

Chem.

Comm.,

1966, 212.

349

P.

E.

Baikie and

0.

S.

Mills,

Chem.

Comm.,

1966,

683.

350

E.

0.

Fischer,

H.

Riihle,

E.

Vogel, and

W.

Grimme,

Angew.

Chem.,

1966,78,

584.

351

D.

E. F.

Gracey,

W.

R.

Jackson,

W.

B.

Jennings,

S.

C. Rennison and

R.

Sprott,

Chm.

Comm.,

1966, 231.

352

0.

L. Carter,

A.

T. McPhail, and

G.

A.

Sim,

J.

Chem.

Soc.

(A),

1966, 822;

G.

Huttner,

E.

0.

Fischer, R.

D.

Fischer,

0.

L. Carter,

A.

T. McPhail, and

G.

A.

Sim,

J.

Organometallic

Chem.,

1966,

6,

288.

353

F.

Calderazzo,

Inorg.

Chenz., 1966,

5,

429.

354

E.

0.

Fischer and

S.

Breitschaft,

Chem.

Ber., 1966,

99,

2905.

987.

metallic

Chern.,

1966,

5,

583.

Chem.,

1966,

78,

112.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

238

INORGANIC

CHEMISTRY

substitution

of

carbonyl

groups

in

arenechromium tricarbonyl complexes

described.

355

The reaction

of

hexamethylbenzene with metal chlorides

of

Group

IV

and

V

in the presence

of

aluminium chloride and aluminium powder

gives

a

series

of

new n-hexamethylbenzene derivatives,

Nb2[

(HMB),],Cl,,

[Nb,(HMB),Cl,]CI, [Ta,(HMB),Cl,]Cl, [Ti,(HMB),Cl,]Cl, and

[Zr,(HMB),CI,]Cl. The reduction

of

dibenzenerhenium cation and the

corresponding hexamethylbenzene complex with sodium in liquid ammonia

yields arene-cyclohexadienyl complexes, but with lithium at

200 Oc

reduction

of

the metal occurs and a paramagnetic complex [Re(HMB),] is formed; this

has also been converted into

a

diamagnetic dimer, [Re(HMB),],.357 The

cation

[bis-(6,6'-diphenylfulvene)cobalt]

+

has been obtained, and

is

the first

example

of

a

molecule with two fulvene groups not containing carbonyl

groups.35*

s65

W.

Strohmeier,

G.

Popp,

and

J.

F.

Guttenberger,

Chem. Ber.,

1966,

99,

165.

356

E.

0.

Fischer

and

M.

Riihrscheid,

J.

OrganometaElic

Chm.,

1966,

8,

53.

967

E.

0.

Fischer

and

H.

W.

Schmidt,

Ber.,

1966,

99,

2206.

858

E.

0.

Fischer

and

B.

J.

Weimann,

2.

Naturforsch.,

1966,

21b,

84.

Published on 01 January 1966. Downloaded by University of Oxford on 04/09/2013 10:41:37.

• V. C. Farmer
• F. Palmieri

The infrared spectrum of a mineral is a characteristic feature, which permits the identification of mineral species. The absorption bands arise from vibrations of the atoms or ions in the structure, and the frequencies of vibrations are dependent on the mass of the atoms, the restraining forces of the bonds, and the geometry of the structure. As a result, the spectrum of a mineral is sensitive to isomorphous replacements in its structure, as these affect both bond strengths and atom masses. The symmetry and regularity of a structure play an important part in determining the intensity and frequency of its vibrations, so that the infrared spectrum is often a sensitive indicator of the degree of order of a crystalline mineral. Amorphous structures absorb infrared radiation as strongly as crystalline structures, although their absorption bands are broader and show fewer distinctive features. Nevertheless, infrared spectroscopy is one of the few techniques which can yield information on the structure and composition of amorphous phases.

The general principles of the concept of oxidation state stabilisation are formulated. Problems associated with the preparation and provision of the highest valent forms of transition elements are considered. The empirical data concerning the synthesis of new compounds of rare-earth elements and d elements in unusually high oxidation states are analysed. The possibility of occurrence of the oxidation states + 9 and + 10 for some elements (for example, for iridium and platinum in tetraoxo ions) are discussed. Approaches to the realisation of these states are outlined and it is demonstrated that solid phases or matrices containing alkali metal cations are the most promising systems for the stabilisation of these high oxidation states. Selected thermodynamic features typical of metal halides and oxides and the regularities of the changes in the extreme oxidation states of d elements are considered. The bibliography includes 266 references.

• Yu. M. Kiselev

Stabilization of oxidation states (OSs) for transition elements is considered. Distinctions between methods for stabilizing OSs in compounds in solution and in a solid state are discussed. The factors influencing stabilization are elucidated. Generation of high OSs of metals in alkali solutions is noticed. The specifics of stabilization of high OSs in solid compounds, including those in which mixed-valence effects are observed, and in solid matrix systems, in particular, in perovskite-related ones, are discussed. New data are cited concerning the stabilization of metal OSs in trans-dioxo complexes [MO2L4] 2 z , where M = Mo, Tc, Ru, W, Re, or Os; and in the paramagnetic clusters that were discovered in neutral tungstates and hydroxo complexes of Rh, Ir, Pt, Pu, or Fe, and other elements in unusual high OSs.

The Bacillus subtilis oxalate decarboxylase (EC 4.1.1.2), YvrK, converts oxalate to formate and CO2. YvrK and the related hypothetical proteins YoaN and YxaG from B. subtilis have been successfully overexpressed in Escherichia coli. Recombinant YvrK and YoaN were found to be soluble enzymes with oxalate decarboxylase activity only when expressed in the presence of manganese salts. No enzyme activity has yet been detected for YxaG, which was expressed as a soluble protein without the requirement for manganese salts. YvrK and YoaN were found to catalyze minor side reactions: oxalate oxidation to produce H2O2; and oxalate-dependent, H2O2-independent dye oxidations. The oxalate decarboxylase activity of purified YvrK was O2-dependent. YvrK was found to contain between 0.86 and 1.14 atoms of manganese/subunit. EPR spectroscopy showed that the metal ion was predominantly but not exclusively in the Mn(II) oxidation state. The hyperfine coupling constant (A = 9.5 millitesla) of the maing = 2 signal was consistent with oxygen and nitrogen ligands with hexacoordinate geometry. The structure of YvrK was modeled on the basis of homology with oxalate oxidase, canavalin, and phaseolin, and its hexameric oligomerization was predicted by analogy with proglycinin and homogentisate 1,2-dioxygenase. Although YvrK possesses two potential active sites, only one could be fully occupied by manganese. The possibility that the C-terminal domain active site has no manganese bound and is buried in an intersubunit interface within the hexameric enzyme is discussed. A mechanism for oxalate decarboxylation is proposed, in which both Mn(II) and O2are cofactors that act together as a two-electron sink during catalysis.

ResearchGate has not been able to resolve any references for this publication.

Source: https://www.researchgate.net/publication/255742513_Inorganic_chemistry

Posted by: bernardolilliee04173.blogspot.com