Chapter 3

ChemistryReviews, 66 (1985)119-189 Elsevier SciencePublishers B.V., Amsterdam -PrintedinThe Netherlands

Coordination

'Chapter

3.1

BORON

3.1.1 3.1.2 3.1.3 3.1.4 3.1.5 3.1.6 3.1.7 3.1.8 3.1.9 3.1.10 3.2

3.2.1 3.2.2 3.2.3 3.2.4 3.2.5 3.2.6 3.3

3.3.4 3.3.5 3.4

3.5

FFFERENCES

George

Davidson

3

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .._.......

. . . . . . . . . . . . . . . . . .._..........................

Compounds containing Ga-C Bonds . . .._..........._. Compounds containing Ga-N or Ga-P Bonds _..._...*. Compounds containing Bonds Between Ga and Group 6 Elements . . . . .._................_._....._. Gallium Halides . . . . . ..*._..............*.*._..... Other Gallium-containing Species . .._............. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .._.........

Compounds containing In-N, Compounds containing In-O, Indium Halides _._._._._...

In-P or In-Sb Bonds . . . In-S or In-Te Bonds . . . . . . . . . . ..*..._....._...

120 120 121 127 128 132 134 138 142 144 153 153 153 154 156 159 164 167 167 167 168 168 170 170 171 171 172 173

. . . . . . . . . ..*.*.*...

173

Thallium(I) Compounds . . . . . . . . . . . . . . ..*......._... Thallium(III) Compounds ._._..... . . ..*._._._._.I.

173 176

THALLIUM

3.5.1 3.5.2

OF GROUP

Aluminium Hydrides . . . . . . . . . . . . . . . .. .. . . . . . . . . . . . . Compounds containing Al-C or Al-Si Bonds . . ...*.*. Compounds containing Al-N or Al-P Bonds . . . . . . .._. Compounds containing Al-O, Al-S or Al-Se Bonds . . . Aluminium Halides . . . ..f._........................ Other Aluminium-containing Species . .. . . . . . . . . . . . .

INDIUM

3.4.1 3.4.2 3.4.3

ELEMENTS

Boranes . . . . . . . . . . . . . . . .._..._.................... Borane Anions and Metallo-derivatives . . .._....... Carba- and other Non-metal heteroboranes . . . .._... Metallo-heteroboranes . . . . . . . . . . . . . . . . . . . ...*..... Compounds containing B-C Bonds . . . . . . . . . . . . . . . . . . . Compounds containing B-N, B-P or B-As Bonds _..... Compounds containing B-O, B-S or B-Se Bonds I..... Boron Halides . . . . . .._. . . .._._._............_..... Boron-containing Heterocycles . . . . . . . . .. . . . . . . . . . . Boron Carbide and Metal Borides .. ...... .. ... .. .. .

GALLIUM

3.3.1 3.3.2 3.3.3

3

. . . . . . . . . . . . . . . . . . . . . . . .._..............*....._.

ALUMINIUM

119

. . . . . . . . . . . . . ...*......*.*

l

. . . . . . . . . . . . . . . . . . . . . . . . . . . . ..._._..._.....*.**_.

OOIO-8645/85/$24.86

0 198SElsevierSciencePublishers B.V.

178

120

3.1

BORON

3.1.1

Boranes

A fully

numerical

Hartree-Fock

diatomic molecules, 1 BH. A set of full

CI

using

plus

a double-zeta

correlation the

leading

Preliminary

calculations

+ Hz + BH+(B' 'C+)

B+('S)

+ Hz + BH+(A271)

for the

A new

method

polyhedral

A systematic

capped

and

(including

role

A method devised and

of the

in transition

from

The

been

solvent

(1) and

canonical

given

now

notations

of the

described

a 3-21G

of

ccmplexes

etc-

for

extended

mechanism

but

the BH3

B2H6

basis

never

their

hetero-

on the

course

for hydroboration

H20

becomes

in organic

coulometric

polyboron

is essentially

olefin.

in

an SN2

plays

no major 7 wholly free.

solvents

titration

4

to include

set)

(a model

H3B.0H2

for

application

carbaborane

been

(2).3 numbering,

structures, 6 derivatives.

and

by

of the 8

of B2H6

with

rings

on a series in their

amplitude

magnitude

of

the most

has

been

of B2H6-ether

aromaticheterocycles,

with

only

one nitrogen

frequently

occurs,

containing

one

per .ring, have via

intermediate

formation.

Calculations

large

has

Hydroboration 9

adduct

that

surface are

non-closed

the

state,

six-membered

suggest

at

complexes.

studied.

borane

of the

potential

linear

metal

(using

that

a study

reactions

or more

were

with

for determining

B2H6-DMF

unique

analogues

calculations

displacement

for BH,

calculations

geometries

the

nomenclature

systems 5

show

of the Czv )

for

anions,

of ethylene

solvents)

99%

SDTQ-CI

in reactions

and

systems,

metallo-)

Ab initio of reaction ether

basis.

for

. . . (2)

proposed

structural similar

reported

for

limit

. ..(l)

Examples

borane

polyhedral

been

using

developed

+ H

been

clusters.

been

Hartree-Fock

+ H

descriptors

to boranes,

hydrides

by

intermediates

has

stereochemical

this

polarisation

is obtained 2 examined.

B+(lS)

favoured

has

ab initio calculations -that bent (C2v or near

suggest

has

an improved

energy

geometries

BH2+

approach

to

as the

of boranes,

crystals

molecular lattice

the

from

potential

reorientations energies. 10

are

B2H6

up to B20H16,

energy

barriers

of the

same

for

order

of

121 11

B n.m.r.

relaxation CH3CN,

data

times

fall

in the

and X = Cl-
Protonation or 61, has

on quadrupolar

been

affinities,

and

(II = 3,4,5

studied

by MNDO

that

cNMeH2

the

c NH3<

2-CB5H9; sites

B4H10 and

B-B

B 4H 1o, Bn~,+4

101,

CB5H9,

B,H,

calculations.

The

structures,

were

edge

(n = 2,5

(n = 4,6

or

calculated

proton

reported.

The

7),

for B6H10 and 221,6-C2B4H6; B-B-B face protonation for B6H6 I 2,4-C2B5H7 ' B7H7 and 1,12-'Z2B10H12; proton attack yielding a three-centre B-H2 bond for B2H6,

predict

show

X = NMe3dNMe2II

carbaboranes,

or

and protonated

calculations

sequence

in B3H,X


boranes

C2BnHn+2

relaxation

and B5Hg;

formation

of protonation

substrates. 12 performed.

carbon

protonation

of a two-centre correlate

Some

the

protonation

3-21G

with

&

with

various

to give

excellent

boranes.

These

as a catalyst

yields are

were

intramolecular 65Oc.

One

from

while

basal

Exchange when

terminal

A one-step

is one

one

that

Borane

Nb2C110

of three both

and NbC14

and

modes

suggested,

were

to the

been

based

apex

attack

was and

important.

from

1H n.m.r.16

i.r.

quantitative

oxidative 15

and Nb(V)

a PtBr2-

produced,

Metallo-derivatives hydridotris-

to occur

1,2'-[B5H8]2,

in essentially

isomers

K{NbC15[HB(~z)3]

migration

only 14 groups.

for

several

below

appears

their

e.g.

for

of the molecule.

are

with

of B5HS

terminal

allows

metal

to produce

on

to basal

energy)

reported

of ~~~~

assigned

acts 13 agent.

at temperatures

bridging

of pentaborane

possible

react

salts

(l-pyrazolyl)borates, uBH

from

electrophilic

at the

Anions

pyrazolyljborate

were

identified

of the migrating

has

Pd(II)

pathways

(of higher

apex

alkenylpenta-

and

positions the

of PdBr2,

oxidising

Two

of

also

derivative&

2H n .m .r .

The

1-butene)

in which

of an additional

were

second

synthesis

Only

suggesting

etc.

"B

amounts

propylene,

reactions

and

structures

deuterium-labelled

dehydrodimerisation

of pentaborane(9)

3.1.2

the

a substituent

yield.

by

B H

were

2-substituted

such

for movement

involving

catalysed

absence

exchange

allows

positions,

first

of various

studied

electronic

calculations

of catalytic

l- and

1,5-C

for B4H4 2 '-5.

bond

(e.g. ethylene,

of

the

in the

Rearrangements in Et20

alkenes

the

initio

Pentaborane(9) , in the presence reacts

B-H

for

addition

hydridobis(land Nb(IV)

1, Nb2C16[H2BJpz)2]2

spectra,

and

structures

122

reacts

B2H6Fe2(C0)6 form

a new

single

crystal

"butterfly" structure The

X-ray

fragment

with

with

orbitals

boron

a BH2

in terms of the

the

five

special 17 fragment.

I2

The

HFe4(C0)12CH.

foux-atom

cluster

62-electron

electrons. iron

properties

by

(A).

"wing-tips",

isoelectronic

to the

to

an HFe4(CO)

or as a saturated,

respect

at 25OC

characterised

contains

as an arachno-,

of the

Fe4

was

This

contributing

with

BH2

in pentane

This

bridging

atom,

ligand

of the

Fe2 (CO)9

to the

can be described

orientation explicable

BH2

similar

an interstitial

complex

excess

HFe4(C0)12BH2.

crystallography.

is closely

compound

with

with

ferraborane,

The

"butterfly"

of the

is

frontier

'H'

(1;) The

compounds

M(BH3Me)4,

using

synthesised,

where

reaction

M = Zr,Th,U

(3).

The

or Np,

molecular

have

been

structures

were

C6H5C1 MC14

+ 4LiBH3Me

determined

by X-ray

tetrahedral hydrogen

possibility

found

give

LiMe3CBH3

in good only

LiPhCH2BH3-

four

Np,

at low yield,

TMEDA

could

be

NH3

loss,

BH3Me

groups,

are:

synthesis

investigated

LiR4_nBHn

via

with tridentate

2.335+0.0032;

although

, except RLi

some

that

forms

Th,

organotriof organoRLi with

n = 0 is not

higher

proportions

e.g.

LiMe2CHBH3

LiBH4

is always

RLi

above 80°C, 19 formed. containing to electron

producing

lithium

reactions or BH3.NMe3.

temperatures,

leads

Zr,

of by

BH3.SMe2

BH3.SMe2,

of solutions

in liquid

and proton

with

are monomeric,

2.487+0.006%18

BH3.THF,

With

reacts

photolysis

(Bu~O)~BHanions,

R.

especially

BH3.NMe3

U.V.

with

all possible

for bulky

LiRBH3,

was

All

distances

of a general

LiRBH3,

compounds

BH3.THF

by

The M-B

. . . (3)

+ 4LiC1

diffraction.

U, 2.49+0.022;

hydroborates, lithium

M(BH3Me)4

coordination

bridges.

2.56+0.05& The

>

borane

but

and present.

LiPhBH3.TMEDA

BH4-,

BH3CN-

detachment radical

an'd

or from

anions

the

e.g.

of

123

‘BH3

-

.

20

Ab -- initio calculations on LiBH4 and NaBHq are consistent with a 21 non-rigid model for these molecules. 60CO y-rays at 77~ produces a Exposure Of Na+BH4- or Na+BD4- to species with large proton hyperfine coupling to two equivalent protons (or deuterons) and a small coupling to two other protons (deuterons) , together with a strongly anisotropic coupling to 1lB . These are consistent with the formation of a .BH4 radical of C2v 22 symmetry (cf. D2d geometry for the isoelectronic sCH4+). A single-crystal that the molecule

neutron diffraction is monomeric,

tridentate BH4- coordination. determined:

study of Hf(BHq)4

shows

with rigorous Td symmetry, and The following bond lengths were

Hf-B, 2.281(8)2; Hf-Hbr, 2.130(9)2; B-H,,,, 1.235(10)&

B-Ht, 1.150(19)K23 Co2(BHq)2[Ph2P(CH2)5PPh ] .O-5C6H6, one of several intermediates in reactions involving Co 'I? NaBH 4 and a, w-bis(diphenylphosphino)alkanes, is a phosphine-bridged binuclear species in which each of the two BH4 groups also bridges the two Co(I) units by a new type of bond: M-H-BH2-H-M. A further unusual feature of the structure is that one hydrogen atom of each of the two central BH2 groups also acts as a bridging ligand. This central unit is thus (2).24

7 H--$----H /AH\\ cio\H/so H\$-H I!

AG* for the fluxional process in [(MeO)3P]2CuBH4 was estimated from data on [(MeO)3P]2CuBH3(C02Et). The difference in AG* for the copper complex, compared to the bidentate vanadium complex is thought to be due to differences in B-H bond strengths rather than differences in geometry. 25 CO2 and COS react with (R3P)2Cu(n2-BH4) under very mild conditions to form (R~P)~CU (T~~-oXCH), where X = 0 or S, 26 An X-ray StrUCtUre determination for Sc{n-C5H3(SiMe3)2)2(U_H)2BH2 confirms the bidentate bonding of BH4-, with the Sc...B distance

124 2.52

The

(3) 2.

rapid Pr,

analogues

with

bridgingsterminal

Nd

and Sm the

Lanthanum LaC13

and

(M = La

adducts

&

NaBH4

BH4-

units

or Ce)

vacua

at

are

can

DYI Ho, Er 29 or Lu).

A theoretical

and

study

calculations

at the

is preferred.

experimental The been

valence-level measured

assignment also

proposed

m-0.

gas-phase was

and

based

as a side-bound

the

opposite

r-lobe

from

on the

the

Fe-C

Thermal salts

confirm

that

He1

with

(Ln =

initio

(Ln = Yb

m.o.

a single,

bent

details very

spectrum

compound,

of the 30 well.

of Cp(OC)2Fe-B2H5

and NeI

radiation.

of model

compounds,

compared

has The and

with

The B2H5 ligand can be an;_C2H4* B2H4 , as a IT-ligand, with a proton (3).

as the

interaction

transformations , in the

NaLn(BH4)4.3DME

other

on spectra

the metal,

bonding,

of B3H8

react

B2H5-

considered

effect

from

NaLn(BH4)4.4DME

reproduced

with

on the

free

chlorides

e

level

La,

Non-solvated

of B2H7-:

However,

For

crystalline

amorphous

made

are not

calculations

(OC)4Fe(C2H4)

been

place.

but

tetrahydrofuran

(DME) to form

photoelectron

in the

from

Lanthanide

MP2/6-31G*

structure

takes 27

solvent.

the ether-soluble

has

bidentate,

can be prepared

be prepared

100-110°C.28

B-H-B

bridge

tridentate.

(Ln = Gd or Tb),

or Tm),

also

exchange

in an aromatic

in 1,2_dimethoxyethane

NaLn(BH4)4.4DME

are

tetrahydroborates

and NaBH4

M(BH4)3

or Yb

hydrogen

cerium

or CeC13

Y

Fe-B

in the

have range

The proton

a significant

interaction

C2H4

been

has

is quite complex. 31

studied

100-280°~.

for

in

the

Na+

different

and

NMe4+

of lower members of the series of polyhedral ions, e.g. B6H6 2- , requires higher temperatures than for higher members, e.g. B12H122 - . ~32 Kinetics of thermal decomposition have been measured for NaB3H8 at

80-100°~

under

decomposition the molar

static

follows

ratio

2:l. 33

isothermal

a first-order The

radical

Formation

conditions. law, anion

releasing

The

solid-phase

B5H9

of triborane(7),

and

HZ, B3H,*,

in

125

is generated by e.s.r.,

by hydrogen

and MNDO-UHF

It was studied from B3H8-. The structure is believed calculations. abstraction

to be cyclic, of Cfv symmetry,with

a single bridging hydrogen,

(4) .34 Os(C0) C1H(PPh3)3

or nido-B5Hg osmaboranes:

reacts under mild conditions with arachno-B3H8-

to form the first-known arachno-[(HOsB

(PPh3)2] respectively.

air-stable

H )(CO)(PPh3)]

polyhedral

and nido-[(OsB5Hg) (Cb)properties of these

The31a B and 1H n.m.r.

are very similar to those of the iridium analogues,

arachno-

[(H21rB3H8) (PPh3)2] and nido-[(IrB5H8) (CO) (PPh3)2]. Mild thermolysis of the 0sB5Hg compound produces nido-[OsB4H8](CO)35 (PPh3)2m The first X-ray diffraction characterisation of a polyhedral metallaborane

osmium compound has also been reported,

(Ph3P)2(CO)&s(PhMe2P)C1&PtB5H7.

for

This has a seven-vertex

nido-

osmaplatinaborane cluster, based on a dodecahedron, with one 5-connected vertex missing, and the metal atoms at adjacent (2,7) positions

in the five-membered

bridging,

(z).36

Bonding in the close-boron to 12, can be considered

open face, linked by Os-H-Pt

hydride anions, BnHn2-, where n = 5

in terms of the sum of all possible,

n(n-1)/2,

boron-boron interactions. The bonding energy, u, between each pair of boron atoms was only taken to depend on the internuclear distance, d, by the relationship:

The scheme can rationallse the details of molecular geometry and can give an assessment of the relative importance of possible

126 37 rearrangement pathways. MNDO calculations were 2also carried out on B H (for n = 6 to 12) to assess the nn accuracy of a recent theory of their electronic structure and intramolecular

bonding this can

(A.J.Stone,

theory also

were

be

Mol.

fully

applied

Phys.,

41(1980)1339).

supported

by the

The

results,

to close-carbaborane

assumptions

and 38

systems.

~~-1,2-(MeCO,0)-2-H-2,10-(PPh3)2-closo-ClIrB8H7~, complex,

has

following

a structure

antiprismatic

containing

rules.

This

structure.

The

Waie's

the

a bicapped

Ir(II1)

theory

an Ir(II1)

a close-ten-vertex

has

cluster,

Archimedean

contributes

three

square orbitals This

and two electrons,

and occupies

a 5-connected

should

with

iso-nidocluster structure -[(PPh3) (Ph2PC6H41 (IrB8H8(0Me)-

be compared

the previously-reported

the

of

vertex.

unusual

species

of

C(OH) )].3g Polyhedron non-degenerate tricapped

tenth

the edge

bonding

thermal

re-examined

under

H2BgC17;1HBgC18 in the

electrons,

as in,

dynamic

At

chemical

of decomposition spectral

data

present.

The

new

include

show 41

that

an overall established vertex

yield

by X-ray

cluster,

characterised, The

crystal

with

g-vertex

products

Some

correct

other

boron

products

Mass B BllClll and B12C112. locllo' the species B,Cl,, where n = 13 to 20,

compound has

from pido-decaborane.

diffraction. non-adjacent

It is the metal

are

atoms

been

prepared,

The first to be

with

structure

was

nido-elevenso

42 structure

boranes,

number

are

no differences

of

[Et4Nf][BllH10SMe2']

shows

that

it has

eleven-vertex, close-geometry similar to those reported for 2, C2Me2BgHg etc. (including metalla-derivatives). B11H9Se3 close-, c 2v, geometry is adopted by all those eleven-vertex polyhedral

used

been

temperature,

at 29.8MHz.

"B-frame", 1 r (Ph2PC6H4)HIrBgHlo]

of 40%,

has

of the halogen-substituted

heterobimetallic,

nido-[(Me3P)2Pt(Ph3P)

were skeletal

to spherical, for - 40 for example, BgHg2 .

ambient

in HBgCl 8 can be resolved

The

closest

The major

shifts

of the

of D3h

clusters

clusters.

(H30)2BloCllo

vacuum.

and BgClg.

B n.m.r.

atoms

also

clusters

of

orbitals

homonuclear

in such

the

decomposition

characteristics

molecular

g-atom

lengths

and

is strongest,

20 skeletal The

and eleventh

trigonal-prismatic

to rationalise bonding

or -antibonding

edge-bonding

carbaboranes 43 of electrons.

and metallacarbaboranes

with

Hence,

the

127 The molecular macropolyhedral interpreted

structure

of the unusual seventeen-vertex

trimetallaborane,

in terms of either

(PhMe2P)4Pt3B14H16,

may be

a formal pentadecahapto-complex

of

a 7,7'-bislarachno-heptaboranyl)-type ligand, coordinated n4, n5 and n7 to three metal centres, or a nido-type 2,7,10-trimetallaundecaborane

cluster

linked to an iso-arachno-6,8tidimetallanona-

borane cluster,

having three adjacent PtBPt vertices in common. Heating nido-B9H12 - under reflux with [OS(CO)~C~~]~ in CH2C12

leads to edge fusion of two borane units to produce The osmium compound probably

forms an intermediate

44

anti-[B19HZ1]' 45

metallaborane.

3.1.3

Carba- and other Non-metal Heteroboranes $11 B 1H) coupling constants in closoThe magnitude of the carbaboranes can be correlated with structural characteristics

such as the number

of adjacent

"umbrella"

Both of these appears to contribute

angle.

cage carbon atoms and the cage

significantly

to changes in the observed

hence smaller

"umbrella"

Gas-phase

pyrolysis

spin-coupling

angles give larger 'J("B'H)

of 1,5-C2B3H5

O°C) gave a complex mixture

in a hot/cold

of products.

boron bonded dimer, 2:2'-[1,5-C2B3H4]2

constants, values.46

reactor

(400°C/

Major ones were a boron-

and a trimer,

2:2',3':2"-

However, a number of [1,5-C2B3H4][l',5'-C2B3H3] [1",5"-C2B3H41. previously unknown species were also identified: a B-C bonded dimer, 1:2'-[1,5-C2B3H4]2, two B-B/B-C linked trimers 2:2' ,1':2"- and 2:2',3':1"- [1,5-C2B3H4] [1',5'-C2B3H3] [1",5"C B H C2B3H4] p and a new tetracarbon nido-carbaborane, 4 7 11‘ Similar studies on the pyrolysis of 1,6-C2B4H6 showed only polymeric products, but a mixture of 1,5-C2B3H5 and4;,6-C2B4H6 gave a good yield of 2:2'- [1',5'-C2B3H4j [1,6-C2B4H5]. The adduct Me3N.5'BrC2B5H6 undergoes quantitative 48 exchange with CH2C12, forming 5-C1C2B5H6. Decaborane(l4)

reacts with sodium nitrite

[9-THP-6-NO,-BloH12]-.

Protonation

halogen

in THF to form

of this with concentrated

H2S04 or dilute HCl gave the azaboranes 6-NBgH12 or 4-NB8H3 respectively. The former yields adducts 9-L-6-NBgH12, with L = Reduction, using LiAlH4 in THF, of Me2S, MeCN or Ph3P. 9-MeCN-6-NB9H12 gave the anion 6-NBgH13-. An analogous series of reactions starting from KHS03 gave 6-SBgHll and 4-SB8H12, while Na2Se03 formed 7,8-Se2BgHg. The structure of 4-NB8H13 was 49 confirmed by X-ray diffraction.

128 Cis-3-hexene

reacts with 6-SB9Hl1,

This in turn reacts with additional temperatures

to give multiple

forming 9-C6H13-6-SBgHIO. cis-3-hexene

hydroboration

at higher

in high yield.

50

Alkyl isocyanides and B9HllE (where E = S or Se) react at room temperature to give initially a mixture of two isomeric BgHllE.CNR compounds.

One of these reacted further to produce a good yield BgHllS reacts with NaCN, of the carbaborane derivative B H ECNH2R. 99 Passage of the latter through an acidic iongiving Na[BgHllS.c~]. 51 exchange column converted it to BgH9SCNH3. Infrared spectra were reported

for solid complexes

rt~-Bl~Cll~C~H~with 0- and N-bases. CH... 0 and CH . ..N hydrogen-bonding Cyclic compounds

containing

1,2-dicarbaclosododecaboranyl

These could be related to the 52 characteristics.

two symmetrically-placed or two 7,&dicarbaundecaborate(lO)

fragments have been synthesised. bridges

of 0' and

These have -S-S- or -S-CH2-CH2S-

(undegraded species) or -S-CH,-SL

or -S-CH,-CH,-SL L

bridges

(degraded species).53 Ph-c-

PhC-c

0

\/

0

BIOHIO

C-C-R' 6

\/ BIOHIO

C-Lithiumcarbaboranes

react with Ln12 (where Ln = Sm, Eu or Yb) to form RLnI, where R = (6). These in turn react with Me?SiCl to give trimethylsilylcarbaboranes and with R'C02H to give (il.54 Thermolysis

of 7,8-C2BgH13

llB n .m .r . spectra confirmed

gives a 10% yield of iso-C4B18H22. the structure previously

suggested

for this, i.e. 3-(8'~-nido-5,6-C2B8Hll)-1,2-C2BloHll.55 3.1.4

Metallo-heteroboranes

The borane adduct, BH3.THF,

and the cobaltacycle

Cp(Ph3P)CoCqPh4

interact to give the nido-cobaltacarbaborane, 3,4,5,6-Ph4-1,3,4,5,6-CpCoC4BH, (8) , in a yield of 20%. This suggests a new general route to carbon-rich metallocarbaboranes. 56 K2C8Ha and VCl-3 react with the nido-carbaborane ion in THF at O°C to give (q'-C8H8)V(Et2C2B4H4). [2,3-Et2C2B4H5] X-ray diffraction shows that the C8H8 is an ne-planar system: it is the first example of such for a first row transition metal other

129

C

Ph

than titanium.

The stability of this compound 2ligands to stabilise the ability of R2C2B4H4

metallic

structures

and metal-hydrocarbon

Thermally-generated carbaborane sandwich

at low temperatures

to give the

l-(n6 -MeC6H5)Fe-2,3-Et2C2B4H4.

structure

Iron

unusual organobonding modes. 57

iron atoms react with toluene and the small

2,3-Et2C2BqH6

ferracarbaborane

can be related to

chloride

was confirmed and C8Hg2-

(arene)-

The expected

by X-ray diffraction.

58

in THF react with Et2C2B4H5-

forming a 1,3,5-cyclooctatriene and 2 minor products,

complex, (n6-CaH10)Fe(Et2C2B4H4), (?16-C6H6)Fe(Et2C2B4H4) and

The main product was characterised by i.r., (C16Hla:Fe(;t2C2B4~4). mass, H and C n.m.r. spectra, and by x-ray diffraction of B, the C,C '-dimethyl homologue. The metallocarbaborane consists of a 7-vertex FeC 2B 4 pentagonal-bipyramidal expected, 59 (n6-CaH10)Fe(Et2C2B4H4) arenes in the presence

cage, as

reacts in turn with benzene

and other

of A1C13,

(n6-arene)Fe(Et2C2B4H4). ring is planar,

fragment

to give the air-stable crystalline X-ray diffraction shows that the arene

centred over the iron atom, and parallel

C2B3 ring of the carbaborane

to the

ligand.

(n6-C8H10)Fe(Et2C2B4H4) reacts with N,N,N',N '-tetramethyl-1,2_diaminoethane, with loss of apical boron, and formation of (n6-CaHl,)Fe(Et2C2B3H5), containing 60 a planar carbaborane ligand. Crystals

of 3-n-cyclopentadienyl-1,2-dimethyl-1,2-dicarba-3-

cobalta-close-octaborane,

1,2-Me2-3,1,2-(n-C5H5)CoC2B5H5,

are

monoclinic, belonging to the space group P21/n. The cyclopentadienyl-substituted cobaltacarbaborane cage has closed, dodecahedral-type geometry, with the C and Co adjacent. 61 the structure proposed from spectroscopic data. The molecular C02C2B5H6]

structure

This agrees with

of 3':2-[2',4'-C2B5H6][l,8,5,6-(n-C5H5)-

has been determined

by single crystal X-ray diffraction.

130 This confirms the structure i.e. a two-cage

proposed

from spectroscopic

complex with a 1,8,5,6-(n-C5H5)2C02C2B5H6

unit linked to a 2', 4"C2B5H6

carbaborane

B-B single bond.

The metalla-fragment

trigonal prism, while the 2',4'-C2B5H6 62 bipyramid. Several products

cage via a two-centre

is based on. a tricapped is based on a pentagonal

from the reaction of One of these was CB8H13-.

shown to be a novel close-iridium(II1) (PPh3)2 -2,10-IrCB8H8. that several pathways

Comparison

species,

l-(PPh3)-2-H-2,2-

with related species

are possible

indicates

for such cage-closure

and that the presence valuable

cobalta-

have been reported

with the arachno-anion

IrC1(PPh3)3

results,

of a varying number of cage-carbon 63 in elucidating such processes.

Nz-5,6-C2B8H12

reactions, atoms is

can be used to prepare the new compounds

nido-9-(n-C5H5)-7,8,9-C2NiB8Hll;

nido_-9-(n-C5H5)-u,o,ll-(Ph3PAu)The 7,8,9-C2NiB8H10 and closo-1,3-(n-C5H5)2-l,2,3,4-CrCCrCB8Hlo. The last structures were determined by X-ray diffraction. compound has a short Cr-Cr distance

multiple

bonding 64

between

(2.272(2)%

- evidence

for

the chromium atoms in this dimetalla-

carbaborane.

Pt2 (IJ-COD) (PEt31

4 reacts with e-5,6-C2B8H12

at room temperature

to produce

in diethyl ether

[9-H-9,9-(Et3P)2-p10

11-H-7,8,9-

This forms orthorhombic crystals, belo;ging to the C2PtB8H10]* space group P212121. The cage structure is close to that of a nido-icosahedron,

with a C?

thought to be hydrogen-bridged,

open face.

The B-B bond is

but the hydrogen

located.

Thermolysis

formation

of [9-H-9,10-(Et3P)2-7,8,9-C2PtB8Hg].

platinum(I1)

species 65

of this compound shows distortion

atom was not

leads to loss of HZ, and towards

This formally a closed octadeca-

hedral structure.

Several new chromium complexes of carbaboranes have been 2prepared. Thus Et4C4B8H8 and CrC12, with Na+C5H5 in cold THF form the red paramagnetic unstable,

CpCr[Et4C4B8H8],

purple isomer of this.

together with an

Aerial oxidation

CpCr[Et4C4B8H8] gives the yellow, unstable small quantity of a green isomer of this.

of

CpCr[Et4C4B7H7],

and a

X-ray diffraction of red CpCr[Et4C4B8H8] and green CpCr[Et4C4B7H7] showed that they had 13-vertex and 12-vertex nido-geometries respectively. Each formally has 2n+l skeletal electrons, appearing to violate Wade's rules (which reguire 2n+4 for nido-geometry). This problem can be

131 overcome

by

assuming

that

at the 66 system.

chromium

atom,

ised

The

deficiency

making

of

3-electrons

it formally

is local-

a 15-electron

nido-7,9(PR ) NiC12 react with nido-7,8-, 2- 3 2 to produce the corresponding icosahedral

complexes

nx-2,

the

9-C2BgHll

bis(phosphine)nickelacarbaboranes

in good

'Heating

yield.

closo-

3,3-(triarylphosphine)2-3,1,2-NiC2BgHll

compounds

solution

[close-3,8-(triaryl-

at

phosphine)* hydrido

80°C

gave

corresponding

-3-H-3,1,2-NiC2B9Hll] Several

ligands.

dimeric

the

+

routes

in benzene

interchange

were

found

of phosphine

for

the

contains

by

single-crystal

a metal-metal 67 groups.

carbonyl

bond

X-ray

This

diffraction,

(2.477(2)2)

and

was

rhodacarbaborane

to contain

(2.725(1)2) there were

two

symmetrically

are

is in the 4 bonds

reported

range

between

for

the

compound.

reflux.

The

vertices.

expected

the

(PEt3)Rh(COD)C1

under

icosahedral

at three

for

BBr3

triclinic

and

a single

approximately

4NOH

Heating X-ray

about

the

bond,

give

[Bu"~N][c~oso-~,~-(P~~P)~ in methanol

Rh-H-Rh

converts

showed anion

this

dimer

temperature

in toluene

cage

5-,

and

CO(~)

carbon-atoms.

in a bridging Trans-[P2 readily of the

The

CbMC12],

undergo

with

is

orange

two

salt

compound. of an NH units. 76

RhCBIOHIO

of Co(PEt3)4

1-Me-4-(Et3P)-u4 The

polyhedral

docosahedron,

unit 7l

with

vertex, lies

exo

or 6 or 7-

framework carbon

adjacent to the

is

atoms

in

to both

polyhedron,

CO(~)-B(7).

where

cage

forms

of

two equivalents

yielding

Co(PEt3J2

M = Pd or Pt;

intramolecular

carbaborane

a new

in a 6-connectivity

position,

It

presence

the Bun4N+

containing

reacts

to be -that of a distorted

4- and

can be prepared

-2-H-l-(NH2)-2,1-RhCBIOHlo].

{Co(PEt3)2-u-(H)2)-1,2,4-C2CoBloHlo. shown

parameters

rhodacarbaborane 69 rhodium atom.

it to

to be

hence

The

in the

this

Closo-1-Me-1,2-C2B10Hll at room

pi.

group

and nido-B10H12CNH3

diffraction

bridged

space

octahedral

RhC1(PPh3)3 Bun

fragments

N.m.r.

two icosahedra. 68

product

distance

closo-3,3-(Ph3P)2-3-H-3,1,2-RhC2BgHll.

crystals,

it

and

The

Rh-Rh

[Ph3PH]+[closo-3-Ph3P-3,3-Br2-3,1,2-RhC2BgHll]from

that

2 metal-bridging

from

shown

of

was

showing

can be prepared C(PRt3)RhC*BgH101* Cs2[7-(7'-7',8'-C2BgHll)-7,8-C2BgHll]

joined

and

preparation

[closo-E3-(u-CO)-8-PPh3-3,1,2-NiC2B9Hll~2].

characterised

or

to form

P cb = g-HCB10H10CCH2PPh2,

metallation

through

exocyclic

compounds

the

B-H

with

bonds

the

unit

132

Pn,

i.e.

Carbaboranyl (RCCLi)BIOHIC

B\M/ [ P2

(sa) and

of

= (g).72

lanthanides

have been prepared

+ [(R-CC-)B~OH~~~L~C~

+ LnC13.3THF

3-n

'Cl

. ..(4)

(10)

@I

lithium derivatives

Compounds

of carbaboranes

containing

The reactivity

and LnC13.3THF,

(41,

B-C Bonds

of borane carbonyl,

that of CH3CO+.

equation

or Yb; n = l-3; m = l-5. 73

Tm

where Ln = La,

The products

anions, BH3C(0)X-, stabilities

.mTHF

from

H-C-C-CH2Prh2 \O/ BloHlo

PCb

($1

3.1.5

(zb), wherecBPT

derivatives

are

BIi3C0, has been compared with

the

(carbonyl)trihydroborate The where X = Cl-, H-, R-, OR-, NR2_' 0".

of this series are in the order:

X = Cl
R< ORCNR2

< o.74 The insertion of boron into an OS-CO bond can be achieved by reaction (S), in which both B2H6 and BH3.NEt3 must be present. BH3.NEt3 (u-H~)OS~ b2O)1o + 4B2H6 cHcl+ 3

(u-H)3(CO)90s3BC0

with approximately Cgv SyEU’netrY. group is close to linearity , with a short B-C distance,

The structure

is (21,

of B+CO back-bonding,

although

. ..(5)

+ H2

this is not reflected (2120 cm -1) .75

The BCO suggestive

in the vC0

which is rather high

wavenumber, 0

C

B Me3Si \

/\ 0 .H, -0s (OC) 3Os I I\ /I

(CO13

he,

HG,," Qy The reaction

-C=B-CMe3 Me 3Si/'\B/

(lg of

methylsilyl)ethene

l,l-bis(tert-butylchloroboryl)-2,2-bis(triwith Na/K alloy in boiling pentane

gives a 60%

133

yield of

(12) , the first compound

The evidence

containing

for this came from n.m.r.,

a B=C double bond.

especially

the chemical

shift of the boron atom.

In addition, the Raman spectrum -1 -1 and 1715 cm with an intensity respectively . 76 ratio of 4:1, assigned to u( 'lB=C) and v("B=C) contained

bands at 1675 cm

co2 (CO1 8 reacts with bis(alkynyl)boranes,

carbonyl R=

n2-alkyne 77 Me or CMe5.

Crystals

of

complexes

tetrasodium

borate)diethyl

(g),

where

tetra-u3 -hydrido-tetrakis(trimethyl[NaBMe3H14.Et20, are monoclinic,

ether solvate,

space group P21/m. structure.

forming dicobalthexa-

with boryl substituents

The Na and H atoms form a cubane-like

is bonded to the boron of one BMe2 group, forming a larger tetrahedron of boron atoms. 78 Compounds

Each hydrogen containing

the very bulky

attached to boron have been prepared, The latter, with NaOH, gives (Tsi)BMe2 is formed. reported. 79

(Me3Si)5C(=Tsi) e.g.

group

(Tsi)B(OMe)2

and

(14).

(Tsi)B(OH)2, while with MeLi,

(Ts~.)A~c~~ and (Tsi)Ga(OH)Me were also

(Tsi)

B

/” '0

D

(14) -

The compounds 1:l coloured n-electrons 80 of TCNE.

BAr2, where Ar = phenyl, o-tolyl or mesityl,

complexes

form

with TCNE.

The triarylborane donates from the phenyl ring to a vacant antibonding orbital

Correlations

of g-, E-, E-, and ‘C(1) carbon resonances in phenylboranes, PhBXY, have been reported. The observed 13C chemical shifts of para-carbons in such compounds show that shielding decreases in the order NHR- NR2 > SR>OR>organyls > halogens. The reverse trend is found for the C(1) 13C chemical 81 shifts. Borane complexes

and arylmagnesium

halides

react to produce

134 arylborohydrides aryl

boronic

(X = Me,

MeO,

synthesis

In Me2S,

however,

"BH2CN"

are

where

a quantitative exists

give

yield

of

as monomeric

oligomers.

readily

aryl

Amines

hydrolysed

= phenyl

constitutes

in tetrahydrofuran

in Me2S with

These

This 82

compounds.

and HCl

equilibrium

yield.

(aryl)B(OH)2,

Cl, Br etc.).

for such

N~[BH~CN]

The

in good

acids,

a very

mainly

was

and dimeric these

terms

solvents

such

of temperature-dependent

rapidly

interconverting

(CH3C5H4)3U(+H3BCN) The

kinetics

hydrolysis e.g.

as CH2C12

pseudo-tetrahedral

isomers:

has

been

independent

3.1.6 ,g that

Compounds initio

planar

form,

(161, by

isoelectronic This

shows

would

have

electrons

containing

a formally localised

H

B-P

form,

in aqueous

two kinds

media, and

of reaction:

or B-As

Bonds

borane,

H2C=N-BH2,

(g),

is preferred over -1 50 kJ mol . This compares

for which

importance

the

and (b) an SN1 mechanism, + 85 of H .

B-N,

about

H2B-0-BH2,

the

via

on methylenimino

orthogonal

for

reaction,

concentration

calculations

a linear,

two

cyano(tripyrrolyl-1)borate

hydrolyse

H+ -catalysed of the

investigated

cyano(pyrrolyl-1)borates

cyanophenyl(pyrrolyl-l)borate,

a special

the

in

(CH3C5H4)3u(NCBH3).84

cyanohydro(pyrrolyl-l)borate (a)

in

in non-

involving

and

adducts,

be explained

equilibria

and mechanism

of several

can best

produced.

to BH2CN.amine

adducts, while, LiCN forms LiBH2(CN)2.83 1 The H n.m.r. spectra of [(CH3C5H4)~(u-~CBH3)]n coordinating

convenient

NaCBH3CNBH2CN].

"BH2CN"

convert

to

or p-X-C6H4,

of B-N

single at the N.

B-N 86

the

planar

form

n-bonding,

since

bond,

a lone

with

show

the with

the

is preferred. the planar pair

form

of

.H \ C=N-B” ’

H'

C=N

\H

H/

\-H H/

An

amino-imino-borane,

three-stage stored BC13

reaction.

as a monomer

or BBr3

forms

(171,

can be prepared

It dimerises in solution

four-membered

for

quite several

cyclic

in good

rapidly,

but

weeks.

internal

yield can

by'a

be

Addition

coordination

of

135

complexes,

(18), -

X = Cl or Br.87

M.o. calculations

suggest

stable, the preferred

that

is thermodynamically

N(BH2)3

conformation

having two N(BH2) units

to them. However, dimers would be more stable than the monomer, especially with bridging Calculations on the species B6(NH2)6 suggest that hydrogen atoms. 88 a planar B 6 ring should be preferred. coplanar,

and the third perpendicular

There is some evidence ArB=NAr

of boron imides,

(where Ar = Ph, 2-Me-C6H4, mesityl

intermediates g

for the formation

in reactions

initio calculations

structure

or C6Fs), as

of the diarylazidoboranes

on [L~BH(NH~)~]+

Ar2BN3.

89

show that the bridged

(19) should be the most stable.

confirms the presence of the B...N The u-v. spectrum of (20) coordinate bond. X-ray diffraction shows that the B...N distance of 162.9(7) pm is only 8.6% longer than that for the formal single 91 (150.0(6) pm).

bond also present in the molecule, An improved synthesis thermal. decomposition

has been reported

of ammonia-borane

attached to a commercial

sublimer

for (H2NBH2)x - by the

in a pyrolysis

tube

to avoid contamination

by

H3N.BH3.

The product was characterised by X-ray powder 11 B F.T, n.m.r. and i-r. spectra. 92 diffraction, Natural-abundance

15

N n.m.r.

an estimate of 1J(15N11B)

measurements

for this molecule

have given 393 (a-45+2Hz).

on B(NHMe)

Tris(methylanilido)borane, (z), crystallises in the rhombohedral space group R3. The C2BN plane is twisted by 37.1° with

136 The B-N bond length

respect to the BN3 plane.

(144.8(3) pm) is at

the upper limit of BN bond lengths in other triaminoborane 94 systems.

Me\N/Ph I

Ph\N/B\N/Me Ah

Ae

(22) -

(21)

B (N=CBU~~)

contains

3

shaped monomers,

"paddle-wheel"

with the

B(NC)3 and NCC~ planes perpendicular to each other, as expected for maximum N"'B r-bonding and minimum But___~ut repulsions. The B-N bond distance benzonitrile

is 1.392.

(PhCH=NBMe2)2,

prepared

from

and tetramethydiborane

centrosymmetric

crystals,

(2:l molar ratio), forms containing (z), with a B-N distance

of

l.59s.g5 Phenyl isocyanate

reactions

with 27 aminoboranes,

PhB(NR2)X,

where X = NR 2, NHR, OR, SR or halogen,

show that the relative

migratory

to boron are in the order:

abilities

nBuNH>Na

>Nz

of groups attached

Me3 >Me2N >Et2N >ButNH >N

; and also RS>RNH>

96 R2N > OR, Ph or halogen. 13C n.m.r. was used to study the effect of substituents free enthalpy

of rotation

compounds PhB(NMe2)X SEt).

on the

about the B-N bond for the series of

and PhB

(NPri2)X

(where X = F, Cl, Br, OMe or

When NR2 is small - the barrier to rotation

is governed

mostly by the mesomeric and inductive effect of X. When NR2 is bulky, the steric effect of X is more important. The rotational barrier decreases with increase in the bulk of NR~. The rotational barrier results mainly 97 when NR2 is very bulky.

from p,-p, N+B bonding,

except

The synthesis of PhB(SEt)NR,L has been reported, e.g. equation (6), where R = Me, Pri, Bus; R2 = -CH2CHMe(CH2) - or -CHMe(CH2)4-. 3 PhB(SEt)2

+ R2NH + PhB(SEt)NR2

13c n.m.r. data are consistent

+ EtSH with restricted

...(6) rotation

about the

137

E-NR2 The the

98

bond. e.s.r.

spectrum 99 atom.

boron

of Et3N+-BH2*

Ab initio calculations several different basis Plesset with

perturbation

double-zeta

polarised

very

Electron

correlation 100

The

close

rotational

theory

geometries,

for both

vicinal

interactions

between

localised

alkylamines four

and

different

Perry

All

for the

adducts.

used

to

from

LiBEt3H,

and

tertiary

sulphur

liberate

R3_,HnN.BH3, in tertiary

bis(borane)

of the

by

B-N

second-order

sets,

basis

data.

with and

electronic

is due

chiefly

to

repulsion 101 structure.

with

for

alkylboranes

(respectively)

NH3,

method;

even

for fair

"B,

the

by

and

Sanderson

isolated

agreement

"B,

products

and BH3

(ii) Jolly

(iv) modified

results

and

alkyl

with

l4 N) ENDOR

of single

experiment

spectroscopy

electron

transfer

(z).lo3

elemental

amines

aminoboranes disulphide

e.g.

microwave

method

barrier

(MP3),

a computed

STO-3G

a closed-shell

-('H,

radical

order

description

different

using

exchange-overlap

method;

(iv) gave

identify

the

gave from

at

M#ller-

third

bond-orbital

(i) CNDO-MO-SCF

reasonable

only 102

on BH3.NH3,

calculated

very

calculated

adducts

and multinuclear

E.s.r. were

NaBH4

were

(iii) MNDO

gave

but

compounds,

was

Pople

from

having

methods:

procedure:

method.

The

bonds

their

a proper

their

arising

sets,

reported

an &I initio and the

out

to the

basis

for

molecules

distributions

out

recently

Despite

to CH3CH3.

Charge

quality

using

it is non-planar

electron-correlated

in BH3. NH3

barrier

experimental

structures,

The

is needed

that

carried

carried

to that

perturbation

compared

been

sets.

method,

geometry

distance.

have

shows

adduct

in ammonia,

hydrogen

gas,

where

n = O-3.

amines

to form

of the

cyclic

and

primary, formation f

and

of the

reacts

NaBH

R3N.BH3.

secondary

with

carbon

O4

phosphorane

is shown

to

138 have

the

The complex is extremely stable, and it (24). compound for which the pattern H3B-N-P-N-BH3 has been

structure

is the

first 105 observed.

Trimethylphosphine at -9oOc

and B4H10,

to -70°C,

to give Very

[H~B(THF)~]+B~H~-. was

then

carried

distribution

out

in terms

of previous

cleavage

reactions.

A detailed Spectra

of

little

in Me20,

patterns

Et20

analysis

has

been

Both

given

states.

Bands

in terms

of C, symmetry.

from

trimethylphosphine

"B6H10".

This

B4H6.4PMe3

was shown

the more 107

to consist

B4Hg.PMe3

was

\B' 1\B--

formed

in THF.

The

a non-rigid to the

form

characterised

3.1.7

and

interactions with

only

B + H20

infrared

and

Raman

and

isomers

trans

were

seen

conformer

form

of a mixture

the

were

species

of B2H4.2PMe3,

-

K

by the new

anion

(25).

M = MO

containing

second-order of B(ls22s22p:

a small

-+ B-OH2

B-O, MBPT

of B4Hg-

is stable

pyramid

boron,

where

reaction

or W; The

+ BO(X21)

H20.

+ H2

O°C.

N.m.r.

with

the

data

phosphine

and

were

spectroscopy.

or B-Se

(~12 kcal.mol -l) barrier

+ HBOH

trimethyl-

products

infrared

B-S

and

L = CO or PMe3,

calculations

2P) with

below

structure, 109

Cp(C0) (L)M-AsMe2.BH3. 1 2 11 by H, B n.m.r. and

Compounds

SCF-CI

of B4H10

Bi-

trigonal

apical

Cp(COj2(L)M-AsMe2, BH3.THF

product rationalised

CH3CH2PH2.BD3

stable

reaction

and B3H5.3PMe3.108

+ L.

attached

the

can be

and hexaborane(l0)

JB

suggest

and

rotational

P

phosphine

the

in THF

The

formed.

the mechanisms

of

and trans

in fluid

was

CH2C12,

CH3CH2PD2_BH3,

gauche

react

and

reactions

about

assigned Excess

and

The

suggestions 106

ratio,

THF.B3H7

Me3P.B3H7

compared.

CH3CH2PH2.BH3,

CH3CH2PD2.BD3.

in 1:l molar

Me3P.BH3,

110

Bonds were

The

used

to study

pathway

in the

B.0H2

(7) proceeds + HBOH

. ..(7)

139

step.

The formation of BO(A2-rr) + H2 111 barriers. Configuration-interaction for

the

first

agreement state

experimental 112 predicted.

Vertical

ionisation

and

applying

X-B=S,

in the

photoelectron

with

towards The

acids

to form

electrostatic Raman contain

lines

(with ~0-0

"LiB02

infinite

assignable -1 cm )

proved

in terms

of its

with

computed

correction

lithium

and the

B60,

values

have

crystal

model

of B60

structure.

with

held

been

has

devised of these

together

by

solutions

anion

in H 0 -2 B(OH)3(00H)

B(OH)4-

and H20.

of peroxoborate

M[(C6H402)2B],

114

in LiB02

has

polymerisation

metaborate

formation

been

reactivity

where

acids

M = Na,

at

K or

characterised. sequence:

to isolate

At 25OC, solubilities + + 117 It Na+>NH4 >K .

potassium

bis(4-methylcatecholato)

, X[(CH3C6H302)2B] I even from solutions small concentrations of (CH C6H302)2B-. Stability the complex were measured. 138

with

CH3

only

constants

B-Cl

(26) -

by

unobserved

-borate(III)

CH3

4

to

theoretical

triangles

in equilibrium

follow

to be possible

2+ C I

polyatomics

distribution

A simple

of B03

for the

prepared

in water

reported

of the

as yet,

to a peroxoborate

Bis (pyrocatecholato)borates,

of these

were

excellent

been

suboxide,

molecule",

of alkaline

at 890

been

the

greater

chains 115

,was no evidence 116 low pH values.

have

linear

The

electron-density

There

NH4,

that

of boron

diffraction.

forces.

spectra

the

gave

position

of the,

of c-boron.

is explicable

in the

higher

of XB=O. 113

properties those

the

perturbation

identification

by X-ray

for bonding units

for

It is believed

room-temperature found

and

These

X = H, F, or Cl, have

spectrum

chemical

compared

been

potentials

where

theorem.

assist

The

data,

much

calculations

of B02.

a Rayleigh-Schradinger

Koopman's will

states

with

was

X-B=0

3 doublet

requires

(27) -

for

140

X-ray on

molecular

structural

determinations

rfac-(OC)3Re(CH3C0)3]BX,

the

triacetylrhenato

chelating however, may

ligand

with

significant

be represented

acts

differences (261,

Both

O(CN)2. symmetry) oxygen with

are

calculated

at equilibrium.

is very

that

low

B203.

of

assemblies

large

significantly temperature, ring

mode

The been

The

B-O-B

of Mg2B205,

and BH 3.THF.

helicity.

these

symmetry

those

of previously

(C2v

at the

central compared

for molten due

based

on

of the B306

crystal

by

(~~"1~0

proposed

X-ray

the

from

bond

X-ray

systems. the

122

Raman

and

shifts . 123

isotopic

B(OCH2C3H4CH0)8B,

study

(space

were

that

P63).

and

it

The

bridges

circular

obtained

disubstituted

shows

group

cyclopropane

and vibrational

compound studied

the B-O

has

of trans-1,2-cyclopropanedicarboxylic

is C3 , with Raman

(MeS2B)20, and

in

"B/"B

to motions

increasing

confirmation

ester:

and

change

up with

in intensity

been

system

of the

do not break

first

hexagonal

Infrared,

spectra

DZ+P)

dicyanoether,

however,

obtained -1 cm are

geometry

diborate

A single

(VCD)

the

reaction

in the

and

structures

is 165.5(12)O,

have

triply-bridged

crystallises molecular

been

units

"bent-twisted"

by the

former

(6-31G**,

to inversion

O-300

and

ring

angle

spectra

novel,

are,

The

of oxybis(dimesitylborae),

assignments

prepared

acid

B306

tentative

infrared

range

It provided

of the

O(B012,

2 kcal.mol-',

have

of atoms, the

The

1.36(2)2,

Some

ca.

spectra in the

structure

obtained.

There

sets

V-shaped

barrier

by the decrease -1 121 800 cm .

at ca.

crystal

length

to have The

that

bifurcated

(E).llg

basis

trioxide,

as shown

diffraction

was

Bands

when

as

out

20 kcal.mol-1.120

Raman

vitreous

symmetry.

extended

for O(B012,

for 0(CN)2,

Low wavenumber

latter

show

vicinal

for X = Cl and Br.

the

Ab initio calculations using have been reported for diboron

C3v

carried

These

as a trioxygen,

approximately

as

been

X = Cl or Br.

where

ligand

have

imposing

dichroism

correlate

cyclopropanes.

with 124

B 0 .S03 and B203.2S03 can be obtained by heating B203 in liquid SO 2125 The infrared and "B n . m . r . spectra of both compounds 2' showed that SO4 and B03 groups were present, as well as distorted B04 tetrahedra. The structures are therefore polymeric. 126 The

interaction

crystalline anion atoms.

of boric

product

(not fully 127

acid

and

dimethylamine

Et2NH. 5/2B203-3H20.

characterised)

with

both

This

at 25Oc

contains

3- and

gave

the

a cyclic

4-coordinate

boron

141 Pb40[Pb,(B03)3C1] The

structure

isolated

B03

Thermal calcium

annealing

PbaO

and have

The

anion are

around

been

formed

interaction studied

isolated.

is formed

along

from

the

by

The

Pb-Pb

for

the

one

inderborite,

crystals,

tetrahedron

one tetrahedron acid

and

a

and

and

space

two

[B304(OH12]~-

Dehydration

and

network

two

diethylene

[NH (c2H4h3)2]

compound

Pbcm.

"dumb-bells",

an infinite

21 axes.

group

[B303(OH)512-

a three-dimensional

of orthoboric

at 25OC. 131

space

orthorhombic

to produce

T1B305 , with

units,

elucidated

containing forms

linked and

crystals,

tetrahedra, 128 ions.

Cl-

hydroxoborate

produces

of B303

been

groups,

These

twisted

The

up from

T1[B304(OH)2].0*5H20

Pnma.

chain

was

planar

orthorhombic

transformations

triangles.

up

is built

magnesium

anion.l*' group

forms

built 130 triangles.

triamine

has

r~~~~07-J~.

4H20

'H

(28) An the

X-ray anion

The

structural possesses

reaction

determination the

boric

gives

as final

aqueous

solution

BOrateS

of ethylenediamine

the

anion

solution. 127aqueous

B 06(OH)4-, 133

and

NaB508.5H20. (M = Na B(OH14-,

160~MHz

solutions

or ICI enabled B303(OH14-

Higher-temperature

n.m.r.

product

spectra

of all

formation

show

that

fluoride

components

have

been

K2B508(0H).2H20, 3 signals constants

that

in

K[B506(0H)4].2H20.133

to their

and B506(OH)4-. spectra

showed

and hexamethylenetetramine,

of KB508. 4H20,

Separation

(28). 32 and potassium

acid

decompose

"B

enH2] [H4B40g] E

structure

of excess

of

containing in aqueous

obtained

for

K2B407.4H20

in solutions

'.

of

or

MB508

to be calculated for 2- was not detected. B405(OH)4 dissociation of polyborate

142 complexes occurs.

B506 (OHI 4

gave a signal due to tetrahedral

boron only, as the trigonal boron resonances Crystals of Na6C03[B60,(OH)6]6.26H20

Pi.

The structure belongs

were not observed.

are triclinic,

135

space group

to the class of soroborates

- consist-

ing of hexaborate groups, between which the cobalt atoms are octahedrally coordinated. 136 The species Na6[Cu2(E_16°24(0H)101] -12H20 also forms triclinic crystals (space group Pl). The structure contains the largest known isolated borate anion. 2+ and encloses two Cu ions.13'

Each

anion is ring-like, A number

of papers have appeared which report studies of phase

relationships

in borate systems.

Li2B407-amide-H20 formamide); 138

These are as follows:

(amide = formamide,

acetamide or dimethyl139 CaB6010-CH3CH2COOH-H20; 140 MgB407-Mg(CH3CH2C00) 141 2-H20, CaB6010-C;:I13CH2C00)2-H20; 143 and KB02-KCl-K2Mo0 ; B203-A1203-Li20; A1203-B203-Na20; B203-CdO-Na20. f44 H3B03-CH3CH2COOH-H20,

EHMO calculations

on B8S16, the porphine

dianion and Cu

2+

complexes

of both macrocycles have beenperformed. The results suggest that the Cu2+ complex of B8S16 may have some stability, but these conclusions depend both upon inclusion of 3d AO's of sulphur in the basis set and upon the choice of semi-empirical parameters for these AO's. 145

B----Se

Dynamic n.m.r. studies on (g), for B-_-X T-back-bonding

evidence

\

R

where R = Me or Ph, provide in the sequence S ?Se '0. 146

3.1.8 Boron Halides The gas-phase reaction of BF3 with Me3N.MH3, where M = Al or Ga, was studied using a combined matrix-isolation i.r. spectrometer/ mass spectrometer. The initial reaction products were BF2H and NMe3; no MH 3 was detected, The reaction is a halide/hydride exchange, not a Lewis-acid replacement. 147 The symmetry of BF3+ in its nondegenerate

ground state is

143 predicted with

to be

the

lowered

second

by two-mode 14 a state.

excited

pseudo-Jahn-Teller

Ab initio S.C.F. m.0. calculations "' The potential minimum occurs BF3_.

have

been

interaction

carried

out

for

for a B-F bond length of -1 149 The calculated barrier to 1.442% inversion is 28 kcal.mol . 15 N and "B n.m.r. spectra were reported for NMe3 adducts of llB_15 mixed boron trihalides. N) all lie within The values for J( a narrow

range,

they

correlate

well

with

S('H),

J(lH-ll B) and J(llB-lgF),

although

less

well

with

as("B)

S("B)

are

complexation mainly give

but

shift)

parameters.

on halogen-induced values

falling

Complexes been

of

reported. very

For

similar,

However,

the

a given

from

the

similar

stabilities

but

with

but

above

and

complexes 151 adducts.

groups

are

re-orient

different

The 4,3,2

stability or l), has

significantly 153 species. Solubility 154 Na or K.

frequencies.

shown

stable

studied

RbBF4-RbX

to be eutectic.

N-m-r.

studies

extensive

ligand

It was

not

halide

compounds.

halogens.

complexes.

slightly

(cZD~)~SO.BF~

non-equivalent

77K,

The BF3

about

the

about

group

its C3 axis

less

show within

their

is rigid

C3 axes, at 77K,

(activation

energy

than

the di-

in the

(X =_F, 155

and

systems

tri-hydroperoxo-

MHF4-MBH4-H20,

Cl or NO3)

systems

? of B2F4/B2 l4 or B2C14/B2Br4 C exchange fn the latter, but

possible

to ass

gn spectra

due

where

have

mixtures less

M =

all been

show

in the

to individual

former. mixed

and 1 Cl react to give an almost 3 4 quantitative yield of B214. N.m.r., infrared and mass spectral data were given for the H214. 156 'H,

l'B,

systems As,

i.e.

BI3

13C and

formed the

150

of the hydroperoxofluoroborates, BFn(OOH)4_i (n = 11, 19 been studied by 'H, F n.m.r. BF3(00H)is ,

more

was

fluorine

other

are

and

dynamically

at or above

135K it re-orients -1 152 kJ.mol .

15.9

for

4-cyano-pyridine

two methyl

the molecule,

the

dependent

pyridines with BF3 or BBr3 have 11 and B n.m.r. spectral data 11 the B chemical shifts are all

stable than the 3-halo-pyridine 1 H and "F n.m.r. studies on Me2S0.BF3 that

containing

(the

infrared

haloborane

suggesting 3- and

curve

4-substituted

and their

and

Species

on a separate

3- or

synthesised,

6(15N)

effects.

S(13C),

31P n.m.r.

between

initial

BC13

data

and

1:l adducts

were

used

Rx(R'0)3_xM0, and

also

to characterise where

subsequent

the

M = N, P or condensation

144 157

products.

Magic-angle

rotation

solid

tetrahaloborates

could

be

resolved.

information

3.1.9 The the

for

suffices so that

It has

a sample

Boron-containing reaction

borirene

of CaK

temperature,

Mass

spectral

probably reasonably

experiments.

stable 159

MeBBr2

under

however,

the

possible

B n.m.r.

from

to obtain

containing

with

evidence

with

the peaks

lines

different

for

ions

detailed

[BClnBr4_n]-r

structural 158 n = O-4.

Heterocycles

(30) both

room

11

to narrow

reflux

structure both

under

in benzene

at room

this

The

reflux

was

also

At formed.

is a 1,3_dlboretene,

borirene

and

gave

temperature.

tBu2C2(BMe)2

that

(2).

BuC-CBut

and

a species

suggested

t

and

appears

in mass

to be

spectral

tBuF7 But tBuTTMIut B

Lie

Ae

(2)

(301 The

first

prepared

3-borolenes, catalyst

2-borolenes,

by the

led

catalytic

(33) r by

The which

system

[(C2H4)2RhCl]

to formation

(32) -

(321, where R = NPr12 isomerisation of the Larger

or Ph,

2CaK/MeBBr2

w

by

been

quantities

of the

li% (34). -

of

(33) -

is trapped

have

corresponding

(34) can

be used

cyclohexene

to generate

to form

(35)? -

Et

Et

Me

(36) -

methy .lborolene,

145

The

compounds

triple-decker where

MM'

oxidised

= F&o,

R,R'

= Me,

complexes

CoCo,

or reduced

reactions decker

(361, where sandwich

CoNi,

to form

NiNi.

charged

were

reported,

including

species

performed

on several

correlated

with

X-ray

results

Et or H, were

related

etc.

The

neutral

to form

complexes

Several

species. the

used

to CpM(p-C3B2HS)M'Cp,

formation

of the 162

can be

other

of the

complexes,

quadruple-

and

(CO)

Mn3

e-

Fe

B-Ph

Fe

(37) The

(38)

thermal

Mn2(CO)lo

reaction

produces

LCpFe(C0j2J2

for the elucidated. 163 The

second

known

can be prepared

of l-phenyl-4,5_dihydroborepin

(37).

forms,

mechanism

(39)

The

among

analogous

other

formation

reaction

products,

example

of the six (8).

-

This

with

(38) and

of the borabenzene

by reaction

with

(39).

was

n-electron in turn

The

not

borole can

form

dianion an

+2tBuLi

B=N

Li2[@-NC

]

. ..(8)

-2%uH

eighteen-electron

sandwich

complex,

acting

as an rl'-ligand

in

(qo).l64 The

oxidation

of crystalline

, pararnagnetic

silyl)-2-methyl-n5-1,2-azaborolinyl ferricenium

cation,

equation

formation of diamagnetic cations. 165 A new

general

route

cobalt

been

l-allyl(trimethyl-

(91, R = Me or CMe3,

, eighteen-electron

has

bis

complexes

reported

for

by the

leads

to the

cobalticinium

the

preparation

of

146

-N

(n5-borolejmetal Ru(C6H6) are

(C6H&

shown

nucleus

than

B-Ph

i.e.

with

All

of the products 11 B n.m.r. (using

[(CzH4J2 RhCl]*.

or

pentahapto-borole

Ru3(CO)12,

rings

The rhodium complex is triple-decked, (41). In 11 B resonance of the central ring is at higher the

complex

field

fi3(CO)lo

to contain

spectroscopy). this

complexes,

that

from

quadrupole

the

outer

relaxation.

ligands, 166

and

e>

less

broadened

by

B-Ph

Cl

e ti

B-Ph

B H

Rh

(42)

B-Ph @

Borinane,

(421,

hydroboration, nonane

(9-BBN),

can

using of

be prepared 2 molar

conveniently

equivalents

1,4-pentadiene,

by

the

of 9-borabicyclo[3.3.1]-

followed

by treatment

with

147

BH3.THF

167

or BH3.SMe2.

-B

xEA

?d (43) -

Radical-initiated

hydrophosphination

diethylaminodialkynylboranes produces The

(g),

arsenic

l-phospha-

derivative 168

derivative.

Non-parametrized borabenzene (BBz)~F~, main

contribute

and

d,(z2)<,d+

that

Na[C5H5BMe] containing

between

arenes.

the

with

PhAsH2

performed

similar

is

The

in the

conformation

sequence ,xy) <

structure

has

to produce

Cf;r)3(NH3)3

to those

: d&(x2-y'

can be rationalised.

favoured

The

4p orbitals

bonding.

"slippage"

on the

delocalised.

and M are metal

dihydro-

complexes

are

complexes

to B)

to the

sandwich

in BBz-

BBz-

observed

the most

anion,

its

Transition

to C than

reacts

E = P or As)

been

to the metal-ring

The

(xz,yz) *

evidence 169 atoms.

and

3d m-o. 's in both

Fe is nearer

some

have

T-electrons

significantly

of predominantly

which

The

interactions

in metallocenes

by excess

calculations

C~H~B-(BBZ-),

2c~.

PhEH2(where

of

or 1-arsa-4-boracyclohexadiene-2,5.

is reduced

m.o.

anion, (BBz)

bonding

using

or hydroarsination

(in

There trans

was

boron

a species

(44).

c

Ql

0

B-Me

1

N-R

Fe

B'

I&

2

[

,:,I,,

(45) (44) (Borinato) (cyclobutadiene)cobalt CO

(c~H~BR) (1,5-c8H12 I

(C4Me4)co(CO)21

and

and

the

complexes

alkynes

R = H, Me or Et,

lithiation

C2R12,

or

from

from

T.l(C5H5BR).171

Bis(2-methyl-n-1,2-azaborolinyl)iron where

can be prepared

at nitrogen,

and

are prepared followed

by

from

related

the

treatment

N-SiMe3 with

species,

(s),

precursor BU~OH

e

(for R =

148 13)

or RX

(for R = Me or Et).

172

co

Crystal

and molecular

structures

of 2 isomers of (461,

[bis(l-tert-butyl)-2-methyl-~-l,2-azaborolinyl~cobalt

have been

One isomer has a clockwise, the other an antidetermined. In both cases clockwise conformation of the azaborolinyl rings. the N-But groups are staggered. closer to the Co than are N or B.

The three ring carbon atoms are 173

L (7

N-R

B/N-R he

Ae

w_g The substituted four-electron

(49)

2-methyl-A 3-1,2-azaboroline

donors

in the sandwich

ligands act as

complexes

(471, where R =

C"e3 or SiMe3, are prepared from (48) and C~CO(C~H~)~ at -78OC. Warming to 20-25OC leads to proton loss and formation of 174 n5-1,2-azaborolinyl complexes, (49). Diboryl compounds, R(C1)B(CH2)nB(C1)R, where R = Cl or Me, n = 2 or 3, and the silylated

or stannylated

or Sn; X = S, NMe, 0, -NMe-NMe-) cyclocondensation

reactions.

species

(Me3Y)2X,

(Y = Si

can be used in (5+1)- and (4+2)-

No thiadiborinanes

are formed, but

varying yields of B/N and B/O heterocycles are formed, e.g. monomeric and dimeric (a).175 13 C n.m.r. spectra have been assigned for (511, and related borazines. a-Charge densities from LCAO-MO Htickel calculations were in reasonable

agreement with experimental

chemical

shifts. 176

149

R-B /=H2-cH'B-R \

N' EJ----Me Me

Me

The reaction of 1,2,4-trithia-3,5-diborolanes not give 1,3,2-dithiaboroles,

as previously

with alkynes does

suggested,

but the

hitherto unknown 1,2,3-dithiaboroles, e.g. (2) ,and R-CEC-R' 177 (where R = R' = Ph, Et etc) produce (53).

(53)

(52) M(CO)5(THF),

where M = Cr or W, react with Bu-B=N-But

(54) I in which the non-planar 178 electron donor.

(oc)

diazaboretidine

is acting

to

form

as

a four-

4MBuy-fBut N-B

\ Bu

tBu/

(54)

(55)

X-ray structural determinations for the pyrazaboles (55) and related derivatives show that the central B2~4 ring can adopt chair, boat or planar conformations - dependent upon the Thus packing effects determine the ring substituents. 179 conformation. (56) is stereochemically non-rigid at ambient temperature,

with

the methyl group located at either C(3') or C(5') of the pyrazole

150

c!B_N&Me c’_N$JMe I

Me

Ihe

ile

(57)

(56) ring.

also

prepared,

and

ylide

complexes

can be

(57) was

Binary

metal

characterised

+4ButLi 2Me2P

-4ButH 2 Me3P

PMe!jBr-

-2LiBr THF

formed

180

by n.m.r.

by the

sequence

(101,

3-NPMe 2 'Li'

rPY2

+MC12 > -2LiCl

. ..(lO)

H2B<;>M

\p/BH2 Me2

where

M = Mn or Co.

Td behaviour different

for the

crystal

The

X-ray 181

structure

shown.

X-ray

structural

R

measurements

at low wavenumbers

A single

where

Magnetic M atom.

=

coordinate.

i-r.

from

the

diffraction

these

confirm

normal

high-spin

are very da analogues.

square-planar

for M '= Mn confirms

determinations

H or Me; 182

show

spectra

have that

been

performed

the boron

the

on

atoms

are

(581, four-

I\ fB\ R2N-0

Intramolecular and

l1 B n.m.r.

The

new

(cH~)~~H,

N-B data

coordination for

the

boron-containing

cH2cooH etc,

was

demonstrated

thexylboronic heterocycles

can be prepared

esters

by dynamic (E).la3

(601, where from

lH

R =

(CH2120H,

salicylaldehyde,

the

151

amine

component

and

diphenylboronic

184

anhydride.

“‘c=$/’ \B_ph Me' I

I 0 -0 Ph/B\ Ph (601 The

crystal

(61) -

structure

of

4-isopropylidene-2,5,5-triphenyl-1,3-

dioxa-4-azonia-2-bora-5-boratacyclopentane The

(61). trigonal

five-membered

and

ring

is almost planar, 185 boron atoms.

tetrahedral

Phenylboronic

acid,

confirms

N-alkylhydroxylamines

the

structure

containing

and

both

formaldehyde

form

of N,N '-methylenebis(N-alkylhydroxylamines), n i The presence of or CH2Ph. where R = Me, Et, Pr , Pr , (G), 'gHll the transannular B-N bond was confirmed by infrared and 'H n.m.r. 186 spectra,

bisphenylboronates

163) The

crystal

structures

of

1 (63), where R1 = R2 = H, or R = these are the first examples of

R2 = CH3, show that 'gHll' coordination complexes derived The

tetrahedrally-coordinated 187 ring. Nitrones forming

e.g.

of salicylaldehyde

seven-membered

(s),

where

from boron

is in a five-membered

react

as bidentate

heterocycles

R = CH3,

2-hydroxypyridine-N-oxide.

CH2Ph,

with

C6H11"

Pinacol(trimethylsilyl)methaneboronate, (trimethylsilyl)methylmagnesium very

useful

synthetic

potential.

chloride. 189

ligands

a B,N-betaine Ph or

OBOCN

in structure,

4-C1C6H4.188

(65), is prepared from It appears to have a

152

x

/O Me3sicH2B10

(65)

Trimeric alkoxydifluoroboranes, (F2BORJ3, react with cyanuric acid anhydrides to form monocyclic acyloxyfluoroboranes such as (6g), where R = Me or Et; R1 = Me, Et or Pri. The crystal structure for R = R 1 = Me was determined - this shows that two conformational isomers of the six-membered ring are present i.e. planar and non-planar. 190

F2kJF i@& 2

@B+j'-

Ph

Ph

:

(67) -

A

(68) -

It has been shown that the previously

reported

1,3,2-dioxa-

borinium cations containing three-coordinate boron are in fact tetracoordinated coordination compounds, i.e. (67), where R = Ph, Me; X = Cl04 or S03CF3, rather than (68). Thus, n.m.r. spectra show four-coordinate to a unidentate

Me

boro

, while

perchlorato

for X = Cl0

infrared bands due f 91 ligand were seen.

iI2 'sL\y/s\Me H2 (69) -

A new boron ring system, 1,4-dimethyl-1,4-dithionia-2,5-diboratacyclohexane, is prepared from Me3N.BH2CH2SMe and methyl iodide, and the subsequent thermal decomposition of the resulting

153 sulphonium state

equatorial.

3.1.10

X-ray

salt.

the

conformation 192

Boron

A study

Carbide

suggested

used

that

into

that

chain

and

a structure

bonding

been

SmB6

with changes 194 composition. The

charge

X-ray

density

atoms the

LiA1B4

metals

3.2

net

than

atoms

distribution

to the

in the

with

is stabilised

electron-deficient

was

by

the

of LaB6,

EuB6

investigated was

found

results

by

to be

analysis around

of

the metal

indicate

charge

transfer 195 framework.

boron

show

of B12C3

in which

a population

The

chain

changing

integration

However, 0.7+ Li , A11°5+ .

CBC

is substituted

one 193

distribution

from

than

for models

ranges

in LiA1B4

charge

It was

stronger

atom

the

only.

charges

structure

solid are

from

that the

ALUMINIUM

3.2.1

Aluminium

Calculations

Hydrides on AlH+

aluminium-bearing AlH3

reacts

cm-?

at 1800

X-ray

used

CaH2

or NaAlH4

produces

structure

trimeric,

a six-membered

that

and

are

breakdown

spectra

exclusion nature

of this

rule,

3).

in THF

P21/n).

abundances 196 to

of

form

vAl-H

is at 1715

as final

ring-chair

of the rule

been

product

carried

mode

conformation.

planar compounds

applies,

in solution. Some

have

For n = 1, the molecule

containing

formed,

Raman

the mutual

centrosymmetric

clouds.

O-3-0.5THF

determinations

(n = 1, 2 or

Infrared

group

Ca(A1H4J2.

H3_nA1(NMe2)n,

3, dimers

and CaC12

space

the

cm-l).1g7

crystal

with

in estimating

in interstellar

(monoclinic,

Desolvation

(vAl-H

were

molecules

with

Ca(AlH4j2.4THF

or

a carbon

charge

electrons. gave

lying

dimensions

Li+~A11'7+)o_g6(B12)1~2~.2Bo~7valence

bonds

of the homogeneity

The net

diffraction.

in the groups

in B13C2.

are much

stable

in cell

that

density-of-states

Calculations

of carbon

made

and

bonds

in which

consists

has

B-C

is more

show

the methyl

of bonding

character.

icosahedron

A study

structures,

The

ones.

both

Borides

in a discussion

multiple-bond

the

band

studies

i.e.

inter-icosahedral

intra-icosahedral

suggest

(691,

and Metal

of electronic

plots., were

slight

diffraction is

For n = 2

n = 2 or

confirming

Solid-phase assignments

for

is

four-membered with

out

rings. 3 show

their spectra

were

show

proposed.

a 198

154

AlH3.NEt3 The

NEt3)2. dimer

A new

simple

method

LiAlH4

has

reacts

as the

primary

CO2

Interaction

been

ether,

octasolvate

S~(A~H~)~.

4DG

(Cp2TiC1)2 compound

10°C.

thought

pOlynUClear

successively.

in THF,

of Cp2TiA1H4,

500K

system

-65OC

form

side

in sites shift 276

atoms of

3-,

initio

Al-CO+

are

M.O.

LHCH

found

to be

ppm;

calculations

5 C.N.,

on Al+/CO

and

(using

in conjunction

the

lowest-energy

that

calculated = 105.5O.

the bond The

CH2

and

distances terminal

geometry

the

SCF

and

the

The

ppm.,

interaction

double-zeta with

formed

as follows:

112-126

are stable , but that (ca. 20 kJ.mol -1) . 205

calculations

in A12CH2

The

were

species

(with

coordination).

146-167 204 0 ppm.

low

sets,

group,

ranges

g-fold

to

a stable

also

compounds

and Al-OC+

very

basis

5- and

4 C.N.,

(Al(acac)3)

are

4-,

(S(27 Al))

ppm;

&

in organo-aluminium

- di(2-

to +lOO°C.

groups

3.2.2 Compounds containing Al-C or Al-Si Bonds 27 Al n.m.r. was used to probe the coordination aluminium

chemical

3 C.N.,2566 C.N.,

suggest

that

stabilisation

(DZ) and

DZ + polarisation

CI methods)

suggest

A12C

are perpendicular,

Al-CI

structure,

both

energies

has

planes

for aluminium

arrangement

were

and

explosive

converts

of binuclear

Cp2TiH2A1(C1)H,Cp2TiH2AlH2) 203

CH4

of

of a linear,

Cp2TiH

amounts

the

Sr(A1H4)2

which

consisting

formed

presence

to give

on

on LiAlH4

range

solvents

with

Small

complex

are presumably

is formed,

a complex

It is based

in the

fire-extinguishers

in the

(Y-H-Al),

accurate

deep-violet

temperature

a Cp2YCl

bridges 199

ether.

at about

in aromatic

by e.s.r.

(Cp2TiH2A1C12,

for the

the

These

CO2

) 8DG fto2'

to be

form

characterised

with

studied

and LiAlH4

it to be

bond.

in diethyl

or NaHC03

in the

Sr(AlH at

devised

products.

by using

The

been

Al...CL

l,lO-phenanthroline

with

has

shows

(Cp2YCl.AlH3.-

hydrogen

alcohol

products formed 201 fires.

methoxyethyl)

of this

of LiAlH4

of benzyl and

to give

"secondary"

of solutions

between LiAlH4 2+ 200 Mg .

in C6H6

AlH3.NEt3

a weak,

reaction

cp2YCl

structure

to the

as by

titration

C2H4

with

crystal

bonded

as well

the

reacts

a bridging

that

methylene

(70). 2.0051; Al-AI_, 3.612, with

Al-Al-CH2,

was

calculated

155

to be

ca.

-1

46 kcal.mol

Vapour-pressure

data

higher have

been

collected

MeAlC12.

Ethylaluminium analogues 207 conditions. Hydrolysis of R3A1

Et20

takes

place

in several

R3Al.0H2.

This

dependent

on the

forms with

stable

then

gave

ratio

the excess

R3A1

(where The

R2A10H.

to produce

The

If this

to form

A12Me6,

formulated The

as

where

heterotrimetallic

comparable

Et or Bul)

gives stages

is l:l,

were

then

Me Me I I -Al-Ml Me

R2AlOH

Me I,=-

reacts

_ C5Me5 Me

I Me

M = Rh or Ir,

species,

in

a complex

react

with

(C5Me5MMe3)2A1Me,

(G).20g

amphoteric

carbonyl

1.

then R2AlOH 208 alkylaluminoxanes.

Al

(C5Me5M)2C14,

and

if it is 2:1,

-. Me>M

complexes

R = Me,

first

C5Me5.

f\ Al-

under

Subsequent

R3A1:H20. but

for Me2A1C1

decomposed

steps.

autoassociates,

206

in energy.

ligands

complexes,

Ph2PNRA1R12

inducing

react

facile

with

alkylmetal

migrations.

Thus

Ph2PN-ButA1Et2

and CpFe(CO),Me give as main product the chelated I I complex Cp(CO)FerC(Me)OAlEt2NButPPh2], as well as a little I Cp(CO)Fe[O(CH=CH2)A1Et2NButPPh2]. An intermediate leading to acyl

these was isolated, and X-ray I Cp(CO)Fe[C(Me)OA1Et2NButPPh2].

diffraction This

heterocycle,

C(M~)OA~(E~)~N(BU~)P(P~)~, 210 to a Cp(CO)Fe fragment.

manner

Ph2PNButAlR2

(where

R = Me or Et)

(OC)4&Jn(CH?AlR2NBu=PPh2), CO has

occurred.

an initial further

This

proton

starting

in which migration

transfer material

from (when

showed

consists bounded

from

"R2A120", containing R = Bui. ability

an Al-Me where

group

occurs

Here

the

structure

R = Me)

The

is R = H >Me

Trimethylaluminium

>Et>>Bu

methylates

however,

products

Mn to via

react

with

to give in wki;h

a C-H

to manganese. have

as bridging is (72). i 21r .

of H from

indirectly,

Mn to P.

Et or Bui,

R as well

form

a net migration

is coordinated

R = H, Me,

bridging

in an n'(C,O)

and HMn(CO)5

(OC)3~(&HOA1Me2A1ButPPh2)[PPh2NButA1(~CH2)CH3], bond

it to be

of a five-membered

The

(AsMe202)-

structures

0 groups, order

except

of bridging

to form

[AsMe4]-

for

156

Bui

Bu=

Me3 Pl

'Al' I

BU;

/‘\

/Ed

Me A,/'\AlMe

Bui/*'\,/"'\Bui 2\o/ Al

Al Bui/

2

Me3

'Bui

[Me2A10.A1Me3]2.

The aluminoxane

i.e. K[A12Me602]

and Cs2[A12Me60].

of a planar A1202 213 ring, with AlMe molecules coordinated to oxygen atoms. is found in the decomposition The unusual anion, p1706Me16]-, of two different high-oxygen content organoaluminium compounds, triclinic

crystals,

anion consists

K[A1706Me16].C6H6

forms

space group Pi, while Cs[A1,06Me16].3C6H5Me

are cubic, space group P2 3. The anion consists of an 1 open Al606 cage, capped by the seventh aluminium atom, which is crystals

bonded to three adjacent aluminium

oxygen atoms in the cage.. The six cage

atoms are each bonded to two terminal

methyl groups, Each oxygen while the unique Al is bound to only one methyl. atom is three-coordinate, as the oxygens not bound to the unique Al bridge two aluminium methyl group each. 214 X-ray structural

atoms and are also coordinated

determinations

(Me3Si)3Al.0Et2,NaAl(SiMe3)4 three the aluminium A1(SiMe3)3.0Et2

3.2.3

Compounds

The reduction

have been carried out on

and NaA1(SiMe3)4.2C6H5Me.

atom is tetrahedrally

is monomeric

the tetrakis-compounds interactions. 215

coordinated.

In all The

(with Al-Si 2.478, Al-0 1.9521, while

form linear chains via contact

containing

to one

ion-pair

Al-N or AI-P Bonds

of Me3A1.NC5H4CH3

with two equivalents

of lithium

N.m.r. data for this are consistent produces [Me3A1NC5H4CH3]22-. with the formulation (74), while its visible spectrum suggests 216 that there is significant Aldr+N bonding. PT The crystal structure of the dimer of (Me3P)3CoN2A1Me2 shows the presence

of a four-membered

A12N2 ring,

(75).

The ring is planar,

157

(74) and

217

centrosymmetric.

Reduction

by metallic

(Me2A1.NC5H4Me)2, electronic

lithium

of Me2ClAl.NC

characterised The

spectroscopy.

by

H Me forms 5 $7 ~1 n.m.r., 13C and

lH,

structure

suggested

is

and

(76). 218 -

Me n0

c12

Me3\/Y/H H' *' \lJ

“*'.CMe9 Cl2

(77)

(76) (Me3SiNMe)2SiFNLiCMe3 a dimeric Hydrolysis membered this

of this ring

shows

cleaves

compound

that

the

trans-arrangement

from

RIM

Spectral

data

shows

unsymmetrically the with

crystal

The

first

-6O*C,

form

diffraction with 220

followed

is planar, 219 (77).

to

ring

confirmed the

R =
aluminium form

treatment

with

can

or Et,

a

be

compounds

the

AlNPAlNP also

rings.

in solution.

P,N-coordination ring

ligand

is

For

a P,P-coordinated

present

[C1A1(NMeSiMe2)2]2,

AlC19

of

with

of alkane.

is found the

four-

structure

bis(methylamino)tetramethyldisilane by

to give

evolution

but

six-membered

cycloalumadisiladiazane,

from

crystal

ring

with

is present,

the

The

M = Al or Ga;

in the

trichloride

to produce

substituents,

an eight-membered

conformation.

prepared,

A12N2

P,N-coordinated,

{Me2A1[P(C6H5)212]2, twist

bonds

[(c~H~)~P]~NH,

that

analogous

X-ray

Si-N

[Me3CNHA1C12]2.

where

and

aluminium

[(Me2SiNMe)2SiFNCMe3A1C12]2.

four-membered

CR2MN[P(C6H5)2]2j2,

isomer

with

the

of nitrogen

prepared

gallium

reacts

silylaminodichloroalane,

in C6H6/NMe3

and

Single in in the

has BuLi

been at

at -8O*C.

158 The

structure

show

that

was

shown

it persists

to be

in the

(7J,

and n.m.r.

liquid

and vapour

and mass spectra 221

phases.

1

\/

Cl

’

'Si ,N

The

analogous

disilatriazane

also been reported. 27 29 Al and Si n.m.r.

(21,

1.r.

I

\

system,

and

Raman

N--t,Al

(HNR-CS+2,

and

spectra were consistent with the structure

derivatives where

has 1 NMel 21 13, H, , also

[ClAl(NMeSiMe

spectra,

which was confirmed by single-crystal

Trimethyl

si\N _

/N\il+y

of

Al,

X-ray diffraction.222

Ga or In react

R = H, Me, SiMe3,

CMe3,

with

dithio-oxamides,

in a molar ratio Of 2:1,

to form 2 moles of CH4 and the monomeric bis(dimethylmetal)dithiooxamides, (80). 'H n.m.r., Lr. and Raman spectra show that these exist as two structural isomers, both of which have a planar They molecular skeleton of two fused, five-membered rings. differed in the coordination forms).223

of the two metal atoms

(E- and g-

/N\C//S\, Me2M

I

MMe2

\/\,/ k

Sodium

tetracaprolactamatoaluminate

in benzene

solution.

Two modes

formation of an eight-membered

exists primarily

of dimerisation

as a dimer

are possible

cyclic caprolactam

-

bridge between

two aluminium atoms or the coordination of the caprolactam ligands belonging to two different aluminium atoms to give one sodium atom.224 The new

amphoteric

A1(CH2SiMe3j3

ligand

(Me3SiCH2j2A1PPh2

or A1(CH2SiMe3J2H

and PPh2H

can be prepared

or form

from

A1(CH2SiMe3)2Br

159 This aluminium phosphide

and KPPh2.

monomer/dimer

equilibrium

is unique in existing 225 in benzene solution.

as a

3.2.4 Compounds Inert matrices studied.

containing Al-O, Al-S or Al-Se Bonds containing aluminium atoms and O2 or 0 have been Vibrational spectra were analysed using 160/la0 isotopic

The results showed that Al and O2 or O3 gave UnSymmetriCshifts. -1 bent Al00 (of Cs symmetry) in N2 matrices, with ~00 1337 cm , al, -1 but that very little of this species was formed vAl-0 1091 cm , In both N2 and Ar matrices, some ozonides were in Ar matrices. produced

(with bands near 850 cm -l) .

There was no evidence

for

metal-superoxide species, such as are found for Ga, In or Tl and 226 O2' 3+ were investigated Twelve complexes of 0, N or F bases with Al by -ab initio m.o. calculations at the 6-31G*/3-21G level. The calculated energies of interaction enable the relative binding energies from gas-phase experiments to be placed on an absolute scale, e.g. for A13+---O
the absolute interaction

32r3 kcal mol-l.227 A single-crystal X-ray diffraction

energy is

study has been carried out on

W(n2 -HCrCOA1C13) (CO) (PMe3)C1, from the A1C13-promoted coupling of The Al-0 distance was 1.751(3)2, i.e. CO and W(CH) (PMe3)4C1. there is a significantly stronger Al-0 interaction than in other structures containing Al-0 (carbonyl; acyl) linkages. 228 The reactions of Cr(CO)5PPh2K.2(dioxan) with AlR2Br (R = Br, Me, Et or CH2SiMe3)

give high yields of Cr(C0)5[PPh2(CH2)40A1R2].

crystal structure

determination

showing that the molecule

is dimeric.

Each octahedral

(OC)5CrPPh2-

fragment is linked by an -(CH2)40- unit to two fragments. T,pe central AlOAlO ring is planar, with 100.3(6)& 0-A1-019.7(5)%22g

Al(CH2SiMe3)2 Al-O-Al

A

was carried out for R = CH2SiMe3,

0

+

H3C

CH3

H3C 0 + A1C13

og

A1C13

+

CH3 0 (82) -

160 2,3,5,6-Tetramethyl-p-benzoquinone coordination

complexes,

identified

and A12C16

form two stable

by i.r. spectroscopy

(in the

as (81) and (82). The latter gave a band due to -1 230 the free carbonyl group at 1645 cm .

v(C=O) region)

The crystal structure

of A1(N03)3.9D20

has been examined

by

neutron

diffraction. The crystals are monoclinic, space group P2l/C, and the asymmetric unit contains octahedral A1(D20)63+, 3+ 231 - and 3D20 molecules not coordinated to Al . N03 Fluorosulphuric acid reacts with aluminium tris(trifluoroInfrared spectra acetate) to form aluminium tris(fluorosulphate). show this to have a polymeric structure, with bidentate 232 fluorosulphates, and six-coordinate aluminium. The composition

of volatile

hydrolysis

Crystals

chlorides

of Ag2~14Cl1002]

of A1C13 has

Thirteen

ions of aluminium 233 were identified.

been studied by mass spectrometry. oxide and hydroxide

products

are orthorhombic,

space group Pbca.

They are formed in the AgCl/AlC13

system in the presence

of water.

the isolated

The structure

Basic aluminium solutions aluminium,

contains

chloride

by addition

solutions prepared

of traces

ions

(83).234 can be prepared from neutral

of alkali or by dissolving

The solutions

bridging

metallic

by both methods

contain

The formation of monomeric, tridecameric and polymeric cations. tridecameric cations is favoured by low temperature, low basicity 235 and dilute solutions. Kinetic studies were made on basic altiinium chloride solutions of low basicity using ferrone reagent. The rate constant for the reaction of dimeric ions with ferrone was: K = 0.97 0.06 min -1 . 236 Reaction of activated alumina with aqueous HCl in sealed tubes, above 100°C, gave basic aluminium

chlorides.

X-A1203 was the best oxide

for this prepara-

161

tion . 237

1H n . m . r . studies

aluminium

chlorides

present: with

a) fixed

possible 238

show

of

that

the three

coordination

random

water

molecules

types

and

of water

molecule

b) adsorbed

species,

motion,

in basic

c) H20

molecules

H20 with

are

molecules hindered

mobility.

Interactions groups were

of potassium studied

binds

very

Partial

strongly

Under

to the

and

acid

and

- . 240

for

were

the

interactions

peaks

Complex

formation

investigated

were

- OH-

phenomena

and

preparation

were

carboxylic

acid

solution

crystalline

amides

is slightly precipitate.

temperature systems

Quadrupolar

was

has

coupling

from

- M203

of phase (where

constants

species

by EDTA

in

paths

replacement.245

complexes

Al(OH)3

also

several

orange

an alkaline was

with and

solution

by

formed

when

as a homogeneous,

formation

M = In,

and

was

parallel

xylenol

studied.

of

complexes, 243

(H4L)

for the

blue,

A1203

been

observation

for

Blue Two

For

complexes.

for Al(II1)

supersaturated, 247

dependence

A1203

the

found

found

obtained

hydrated

to study

EDTA.

imidazolidine-2-one

spectrophotometrically.

were

and

1:3 Al-lactate

of semithymol

dissociative)

of

potentiometry.

possible

Evidence 244

blue, semimethylthymol orange. 246

semixylenol

The

in

Al(III),

solutions)

lactate

1:l and

Al n.m.r.

of replacement

studied

aqueous

Al 3+ and

between

by

and hydroxy-lactate

methylthymol

in the

studied

(H L- citric acid). Evidence +3 , AlL, A1L23-, as well as a

make

constants

the

- ion.

234

~~,(oH)~L~]~-.~~~

Equilibrium

The

Al(OH)

binding.

were

between

at 25OC

citrate,

stoichiometries.

kinetics

(associative

with

aquo-lactate 27

by

different

AlL-

this

equilibria

@l(HL)]

for Al(H20)63+,

as mixed

The

the

for AlL', A1L2-, Al(OH)L22241 = salicylic acid). Similar data

(for 10 mM

exchange

as well

with

disrupts

studied

complex

of Al(III)

slow

separate

as

membrane

aluminium

determined

mononuclear

very stable trinuclear 27 Al n.m.r. was used

lactate,

the

groups,

Equilibria

(where H2L for Al 3+ - H3L

determined found

carboxylate

OH- were

constants

and A12(OH)2L23were

in a bilayer

head-

A13+ -1,2-naphthaquinone-4-sulphonate/l,2-dihydroxy-

Equilibrium

was

carbonylated

conditions

complexation

naphthane-4-sulphonate-OH salicylic

with

contained dilute

of K+ by NMe3R+

hydrolysis

system

(as A1C13. 6H20)

dodecanoate

by n.m.r.

replacement

Redox, the

of Al(III)

has been V or Ti). 240

asymmetry

parameters

studied

were

162 determined

from the 27 Al n.m.r.

spectra of single f3-alumina

The temperature dependence of the spectra gave Useful 249 information. 27~1 n.m.r., with "magic-angle spinning", was used solid-phase

crystals.

structural

to probe the environments

of aluminium

atoms in non-crystalline

solids, A1203-Si02 gels, soda glass and mullite precursors. was possible to obtain quantitative estimates of tetrahedral

It and 250

octahedral coordin_ation proportions for the aluminium atoms. 27 Al n.m.r. and the contribution of Al203 to molar refractivities show that the aluminium u-LiA102, but tetrahedrally

is octahedrally

coordinated

coordinated in In B-LiA102, in y-LiA102.

contrary to earlier suggestions, only tetrahedral aluxninium is present. 251 A similar result was reported from a 27 Al n.m.r. study, using magic-angle

spinning, of polycrystalline

LiA102

polymorphs.

The symmetry of the alurninium sites was characterised 252 by quadrupole coupling data. Lithium hydroxocarbonatoaluminate was synthesised by treating Li20.2A1203.nH20

(where n = 7-11) with C02.

The product is

believed

to have a layer structure, based on bayerite, with monoclinic symmetry. 253 27 High-resolution Al n.m.r. of crystalline aluminium phosphates

show that for a wide range of compounds

the aluminium

is

exclusively octahedrally coordinated. 254 I .r 0, X-ray and thermal analysis data were reported for the crystalline tripolyphosphate, 255 Na2A1P3010.4H20. A study of the high-resolution solid-state 29 Si and 27Al n.m.r. spectra has been made for the product of treating zeolite Na-Y with SiC14 vapour at 560°C. of the dry material

synthetic

The 27Al n.m.r.

showed two peaks, one due to residual

spectrum lattice

aluminium,

and one due to A1C14-. The washed, dealuminated zeolite Y gives 27Al resonances due to tetrahedral aluminium in the lattice, and octahedral aluminium as cations in the zeolitic 256 channels. Neutron diffraction on zeolites sodium ZK-4 (Si/Al =

1.65) and sodium Y (Si/Al = 2.61) shows that there is no longrange Si-Al ordering, unlike sodium A and X zeolites. 257 Time-of-flight neutron diffraction data on NdAlO show that NdA103 crystals are rhombohedral, space group Rfc. 2 58 Na20 and AlaO react in a closed nickel cylinder at 980X to form colourless Single Crystals of Na14 A14013 , which are very moisture sensitive. They crystallise in the monoclinic space

163

tetrahedra

14-

anion is built up of four AlO 259 sharing vertices. Basic sodalite,

group P21/c-

The A14013

Na8A16Si6024(OH)2. 2H20 forms cubic crystals, The 1:l alumino-silicate The structure

and ionic distribution

ammonium-hydronium determined

framework

space group Pz3n. 260 is completely ordered. in the Conducting

plane of

B"-alumina,

a solid electrolyte,'were The composition by single crystal neutron diffraction.

is (NH4+) 1 561H3'+) 0.19"g0.75A110.25017 (H20)0 . 25' The structure comprises ipine blocks of aluminium atoms, either tetrahedrally or octahedrally

to oxygen atoms. One of the two 3+ tetrahedrally coordinated Al sites is 37% occupied by Mg 2+ to provide charge compensation in the structure. 261 Differential

coordinated

calorimetric

analysis,

1

H n.m.r.

spin-lattice

relaxation measurements and X-ray powder diffraction data show that hydration of Ca0.A1203 in the temperature range 4-83OC proceeds in three distinct steps. 262 Reaction of aqueous solutions with subsequent

precipitation

of A1C13 and sodium germanate,

as the sulphate,

gives

This was characterised by cGe04Al12 (OH)24(H20)12~7(S04)4.xH20. chemical analysis and Al n.m.r. The new species was shown to have higher stability cation. 263 Solubility,

than the tridecameric

basic aluminium

and the composition

of solid phases, were studied in the system A1(N03)3 - Al2 (S04)3 - H20 at 25OC. 264 Phase relationships were established for the systems: Al 3+ ,Ga3+ + H+II so42- - HgO; Ga3+ + H+,In3+11 S042- - H20, and A13+,In3+11 S042- 265 H20 at 25 C. A12V10028.22H20 forms orthorhombic crystals, space group Acmm. Thermal decomposition yields 2:l mixtures of V205 and A1V04. 266 The temperature partial pressure

of peritectic

fusion of AlV04 depends upon the of oxygen in the synthesis of the specimens. 267

Phase compositions and equilibria were studied in the system A1V04 - CrV04 - FeV04 - NaV03. A continuous complex solid solution was formed, involving NaFeV207, NaCrV207 and NaA1V207. 268 Phase diagrams were elucidated

for the systems: Al 0 - Si02 2 369 A1203 '2'5' Al203 - K20 - V205, A1203 - K20 - SiOz7; V205; Na20 - v205 and. A1203 - SiO - Na20 - V205. A study of phase 2 composition and equilibrium in the system FeV04 - CrV04 - A1V04 KV03 shows that several new pyrovanadates are formed, including KA1V207. 271

164

AlTaO

single crystals

can be prepared

from A1203 and Ta205 at

X-ray diffraction shows that the crystals have tetragonal 18OOOc. 14 The structure is of rutilesymmetry (space group D2h-P42/mnm). 272 type, with a statistical distribution of Al and Ta. The vibrational

spectra of MA1(Mo04J2,

have been studied,

and some assignments

equilibria

have been determined

M2(Mo04)3,

where M = Al or In.274

where M = K, Rb or Cs, 273 Phase

proposed.

in the systems Bi2(Mo04)3

-

The spine1 ZnA12S4 has been studied by X-ray diffraction.

The

lattice constant was 1000.9(l) pm, and the results were The cation distribuexplicable in terms of the space group Fd3m. 275 tion corresponded to the normal spine1 structure. A1(NR2j3

and C1A1(NR2j2,

dimethyldithiocarbamates

where R = Me, insert CS2 to form the

and ClAl(S2CNR2)2 27 Al n.m.r. suggests The former is monomeric;

respectively. coordinate aluminium,

Al(S2CNR2)3

which

is confirmed

six-

by X-ray diffraction

(the

The latter is at the aluminium is distorted octahedral). dimeric, with two bridging chlorine atoms, and six-coordination at 276 each aluminium. geometry

The quasibinary

systems Znl_xCdxA12S4, ZnA12(1_x1Ga2xS4, and were investigated by X-ray diffraction and

ZnA12S4(l-x)Se4x vibrational spectroscopy.

In the spine1 ZnA12S4, up to 20% of

the zinc can be replaced by Cd. In the other systems ZnA12S4 has no measurable homogeneity range. Thiogallate phases have much broader homogeneity reversible 3.2.5

Aluminium

Stability complexes

ranges.

phase transition

At 950°C, ZnA12Se4 undergoes 277 structure.

a

to a wurtzite-type

Halides

constants

have been measured

in the system A1(N03J3

KAlF2+ 2.90 x 106; KAIF

- NH4F - NH4N03

+ 2.76 x lo=,

2

for aluminium

KAIF 3

fluoro

- H20 at 25OC;

1.46 x 1015; KAIF _ 4

6.76 x 1017; KAIF 2- 1.97 x 101'; KAIF 3_ 2.88 x lO28.278 5 6 Standard extended HiLckel techniques, with automatic optimisation, were used to study the structures and energetic9 AlX3 and A12X6 molecules, where X = F, Cl, Br or I. Marked nonrigidity was found for the AlXAlX ring in A12X6. 279

of

The interaction of BeF2 and A1F3, at temperatures 400-800°C and A1F3 concentrations of O-75%, was investigated to give preliminary results on the A1F3-BeF2 phase diagram. 280

165 The

solubilities

of CaCl2

studied

at 60°C

80°C.

identified. isolated The

and

281

The

aqueous are

compounds

cryolite mixed

, where

[C(NH2)3]3MF6

from

in aqueous

solutions

fluoroaluminate

CaNaA1F6

M = Al,

solutions

of the

isostructural,

space

were

relationshios 3R 283 .

and

elucidated

for the

were was

Ga or In, were

corresponding 282 group Pa3. system

fluorides. Some

phase

3Li,3Nall A1F6,3C1,

(Me3C)2Si,N,;:,F,Si(CMe3)2

Meg&. (841 Silicenium aluminium carried The

ylides

out

for

A1(C104)3

by

structure

species

in anhydrous A1C13,

formed

methanol

the

chief

was

studied

species

is

due

anions

cations.

chloro MeOH

and

hexasolvated

solutions complexes,

and H20

1.r.

leads

have

been

obtained

for

Addition of mono-

chloride

vapour

(ca. 1075K),

to 10 atm., including polarisation 35 Cl and 37 cl compounds. Detailed

measurements,

active D3h

of D2h

and A1C13

possible.

fundamentals

monomer

700-50

symmetry

were

The

- all were

studied aluminium

assigned.

assigned. 286 dimer.

in mixtures chloride

dimer

of

vibrational

spectra

9 Raman-active

also

both monomer and 27 Al n.m.r. line-widths

and

All Force

13

C n.m.r.

were and

both

vapour

four fields

temperature,

and

spectra

assignments

interpreted

were

in

infrared-

fundamentals

chemical

The

at pressures

7 of the

l-methyl-3-ethylimidazolium

at room

to the

data on A1235C16 and Al2 37C1 in the 6' -1 cm , as well as Raman spectra of

vapour

therefore

the

with

of 0.3

terms

no

very

di-aquodi-

species,

aluminium

35C1

with

of H20

and

A12C16

were

and

between

473-873K

(ca, 500K)

or

give

ranges

of the

and

27 Al

lH,

solutions

by

AlC13) , including

A1C13

to interaction

formation

was

[AlC12(MeOH)4]+,

chloride-free 285 coordination sphere.

in the

spectra

(A12C16,

followed

by

A1(C104)3

Al(III) to the

with

determination 284

by dissolving

evidence for monochloro-species. 27 Al resonances, probably broad

A1C13

coordination

[(Me3C)2SiNCMe3]2A1C1F2,(84).

of ionic

For

be stabilised A crystal

trihalides.

nature

n.m.r,

can

for

calculated

shifts

l3 C shifts

for

have

chloride were

a

been

and

166 explicable

by anion-cation

interactions,

and the 27Al line widths

by the presence

of more than one type of chloroaluminate ion. 27 Temperature-dependent Al n.m.r. spectra show that chemical exchange takes place between chloroaluminate anions in aluminium chloride-rich molten salts. 287 [A1 (C4H802)

cl31

.‘3H83,

forms monoclinic crystals, space group contains distorted trigonal planar AlC13

The structure P21/m. units bridged by dioxan chairs to form chains parallel b-axis.

to the

The chains are separated by layers of dioxan molecules.

The geometry around the five-coordinate aluminium is approximately trigonal-bipyramidal, with some distortion of the equatorial chlorine atoms (angles 115°-1230),288 High-resolution 1H and 13C n.m.r. spectra have been obtained for the n-butylpyridinium

cation

(BP+) in (BP)Cl-Ale13 melts.

The are affected by

chemical shifts and proton coupling constants BP+-AlC14- association. The 7Li n.m.r. spectra of (BP)Cl-AlC13- 289 LiCl gave evidence for the formation of Li+A12C17 . Component ;:;,;o;;und Complexes

interaction was detected in the CuCl-A1C13 system. C~(Alc14)~ was formed, which melts incongruently at YbC13-(A1C13),

have been investigated in the gas phase radiochemically, using tracer 16'Yb. AH 298 and AS2g8 values were estimated for YbA1C16, YbA12Clg, YbA13Cl12 and YbA14Cl15, from measurements

of the equilibrium

constants

for (ll), in the range . ..(n)

500-lOOOK. The nuclear spins of 27A1 , 6gGa or 71Ga in [MC14_nBrn]- and [M(MeCN)613+, where M = Al or Ga, relax by means of the secondkind scalar and quadrupole relaxation mechanisms. NO exchange processes were found for these ions on the n.m.r. time-scale. 292 PI4+AlI4-

is produced from P13,12 and A1I3 in CS2 solution. It forms orthorhombic crystals, space group Pna2. The anion is approximately tetrahedral , with an Al-I distance of 251.8 pm. Weak I... I bonds (338.6-345.1 pm) link the anions and cations to form a three-dimensional array. 293 P215+A114- crystals are orthorhombic (space group Pbca) , with a mean Al-1 bond length of 252.9 pm. 294 A12Sb2112

is prepared by heating

stoichiometric

amounts of A1I3

167

/I

I\

Sb\

I' I ‘-4’-I,s/yl-I

I I

/\

-1 'I

I/

and SbI3 in CS2. It forms monoclinic crystals, space group C2/m. The A12Sb2112 units are formed by two Sb-I octahedra sharing four 295 common edges with two A114 tetrahedra, (as)3.2.6

Other Aluminium-containing

The electronic

absorption

Species

spectra have been reported

for A12,

and In2. The ground state of Al2 was re-assigned as h+ g, not Ga2 296 3zg' The phase diagram has been established for the Ti-Ni-Al-C The H-phase Ti2AlC and the perovskite phase system at llOO°C. 297 Ti3A1C are destabilised by even small amounts of Ni. Aluminium dissolves in LaNi5 to form LaNi5_xAlx (for x up to 1.5). Hydride phases based on these have been synthesised and characterised. They are more stable than those based on LaNi5 itself.2g8 EXAFS spectra obtained

for solid and for flash-melted

aluminium

films with a single nanosecond pulse of X-rays from a laserThese spectra gave a direct observation of a produced plasma. 299 degree of local order in rapidly-melting aluminium. 3.3

GALLIUM

3.3.1

Compounds

The product benzene

containing

Ga-C Bonds

from the reaction of Ga(CH2SiMe3)3

at 45'C was identified

as KGa(CH2SiMe3)3H

and KH in (by X-ray

diffraction, i.r., 'H n.m.r. spectroscopy, and by its reactions). The compound does not decompose thermally below 200°C. X-ray diffraction shows that the crystals are monoclinic (space group The geometry at gallium was distorted tetrahedral. The P2l/C). infrared spectra of KGa(CH2SiMe3)3H, and its Ga-D analogue, -1 -1 showed VGa-D at 1075 cm , and hence vGa-H ca. 1500 cm - an

168

unusually

low value.

crystals

The

with

(P2 /c), 30b

2.251(4)%

Chlorogallium(III) Grignard o-Ga-C

reagents 301 bond.

3.3.2

Compounds

Ph2GaX.L

reported

and

(X = Cl), Cl) I 304

In-C

new

containing

from

248

(X = Br)

Ga-N

Their

of the

EHPG,

transferrin.

3.3.3

vibrational

The

has

i.e.

site

racemic

been

(X = Cl or Br)

spectra

isomer

were

human

Bonds

and

The

two

Between

on the

This

complex

is a

iron-transport

(monoclinic,

of EHPG.

out

ethylenebis[(o-

Ga(EHPG)2-.

0 atoms

Containing

carried

ligand

of the

crystals

two phenolate

Compounds

a

Bonds

hexadentate

for the metal-binding

the

or

containing

[(Ph3P)2N]+Ph2GaX2-

determination

complex

contain

2.234(4)-

organolithium

species

or Ga-P

and

range

cm'1.3o2

structure

two N atoms,

with

monoclinic

e.g. VGaN in the pyridine adduct is at 262 -1 cm ; vGaP in the PPh3 adduct at 310 (X =

hydroxyphenyl)glycine],

protein

react

K[1n(CH2SiMe3)3~]

formed

in the

porphyrin

Ph2GaX.

assigned,

gallium(II1)

only

distances

porphyrins to form

(X = Br)

A crystal

model

tetrakis-compound

(L = py or PPh3)

can be prepared

and KH gave

In(CH2SiMe3)3

and K[In(CH2SiMe3)4].

space

group

gallium

is bound

carboxylate

Gallium

C2/c)

0 atoms.

and

Group

to 303

6

Elements The Bb,

alkali

Cs;

metal

vibrational K2Li3Ga04

all pm).

oxides.

Infrared

assignments,

were

is prepared

LiGa02/KOo

clinic,

and

M' = Ga; M = Li or Na;

corresponding

from

gallates

space

48

. group

from

of the gallium atoms 305 The interaction

M' = In,

crystals). the

can be prepared

lithium

oxides The

structure

four-coordinate

M = Li,

where

Raman spectra, 304 reported.

while

of

MM'02,

and

the binary

(as single P2l/c,

indates

the

some

(as a powder) crystals

or

are mono-

is complex,

(mean Ga-0

molybdate

from

with

Na,K,

with

distance

183

and gallium(II1)

sulphate

produces Li3Ga(Mo04)3 and LiGa(Mo04)21 as well as 306 Li2S04. CaAGaE07, where A = Ti, Zr, Hf or Sn; E = Sb, Nb or all have the zirconolite structure. 307 Ta, 12-Tungstogallic acid, H5~GaW120401* 13H20, and its alkalineearth

metal

salt.

The

diffraction,

salts

were

compounds

prepared

were

by

ion-exchange

characterised

thermogravimetry,

i.r.

from

the

sodium

by X-ray powder 308 1 and H n.m.r. spectra, etc.

169 Infrared gallium

and

Raman

oxides

except

the

spectra

CaGa407,

third

have

gallium

coordination

state,

the

centrosymtnetric

last

two

An X-ray systems, found Ti,

to refine Gd3Ga5012.

the 311

structural

Pb3GeGa10020

forming

a string

been

for the

calcium

Ca3Ga206.

All

tetrahedral

have 309

made

non-centrosynunetric,

of the

MO2-ANbO4 Evidence

forms

a ribbed

orthorhombic

is four-coordinated

GaX3

(where

(where

ClGa(SR) 2, where and Ga(SR)3, infrared

and

to the

R = Me,

diagrams

in the

Crystals

from

are

(monoclinic

Ga4S10 The ordered

phase

silyl

is a transition

orthorhombic

of

Pnma.

Ga-S

the

The

distances

linked

in pairs,

[GaS41n

the

sharing

space

group

have and

pressure

The edges. 317

group

show

to the NaCl

is built

units.

sphalerite-type.

at high

related

contain 318

(space

been

Pna21),

opposite C2/c)

by

systems

structure

structure.

distorted

chalcopyrite

group

[Sn2Sll]n

is monoclinic

or 8 GPa

the

formation

The

and

adamantane

basic

R = Me or Et,

characterised

for

(space

atoms.

of

the

Ph,

(X = S, Se or Te) case. 316

orthorhombic gallium

Me3SiSR moisture-

Et,

where

were

of glass

in each

crystals,

extremely

I; R = Me,

established

Regions

(X = Se or Te)

from

compound

been

of Ga2Se3

(X = Se)

garnet,

are

sulphides

Br3Ga2(SR)3,

sheets

of the

of CuGaX2

new

are

having

a superstructure

GPa

Br,

As2X3-Gax

four-coordinate

anions,

12.5

have 315

of Ga2Sn2S5

tetrahedra

studies

Ph,

diagrams

alternating

Ba4Ga4Sg10

Et,

the

to give

X = Cl,

systems

equilibrium

containing

react

where

and Ga2S3-Pb.

identified

used

rings

planes

group

with

where R = Me, Et or Ph. All 1 314 H n.m.r. spectroscopy.

Equilibrium Ga2S3-PbS

space

(by S atoms),

Br or I) and

Et or Ph)

X2Ga(SR),

crystals,

These

M =

Pb3GeA110020.

of six-membered

plane. 312

was

gallium

with

was

(where

2.335(1)a.313

X = Cl,

R = Me,

sensitive

and

for gadolinium

is isostructural

of octahedra.

2.215(2)

forms

two

of a framework

gallium

The

first

parameters

between

at

in the

structures. has

and

Zr, Hf or Sn; A = Al or Ga.

consists

by

GaLa30S5

Gas4

the

reported

(orthorhombic) compounds MO2,4GaNbO4 310 or Sn). Single-crystal X-ray diffraction

tetrahedra,

connected

up

only

study

M = Ti,

structure

Ga04

been

Ca3Ga40g

for the new

Zr, Hf

The

while

diffraction

where

have

CaGa204,

isolated

Bb), 319

that

structure

with X-ray

there type

(Te).320

SrGa2Se4

can be prepared

crystals

(space

group

from

Cccm),

SrGa2 and the

and

Se.

structure

It

170 is a new

variant

produced

from

(space

group

tetrahedral ances

are

GaGeTe

infinite

and

two

block

one

germanium

Chemical

H2,

reaction was

were

P4 and P2

with

by

the

It is possible

shows

the

formation

studied range

two-dimensional

atoms

from

GaSe.

(2.656(3)2)

Raman

600-lOOOK,

thermodynamic

Cu,

was

and

Zn, Co or Mn. system

324

in the

for GaCl,

in chloride The

of long-chain

GaC12,

benzene.

melts

results

at ca. were

chlorosulphides,

and

a phase

Ga2C17-_326

(C6H6)3

5Ga2C14 from . crystal structure

The

centrosymmetric

isolated

fragment,

cubic

phase.325

as GaC14-

and

the

found

spectroscopy.

units,

benzene

the

two

molecules.

n6-benzene

In

rings

form

124.4°.327

of gaseous

by visible

gas

up of cyclic,

of

Ni,

for

in the HCl-GaP

sulphur

in anhydrous

angle

= Mg,

Evidence

and

bis(benzene)gallium(I)

The

dist322 250 pm.

and

, derived

calculated

studied

as well

I11c14]2

an interplanar

MI1

formation

it is made

[(C6H6)2Ga1Ga

been

to crystallise

solutions that

GaSe6

It is a semi-

containing

to 3 tellurium

in the

of gallium

(-GaC12-S-GaC12-S-),

Ga2C14

247

elements.

i[Te-Ga-Ge-Ge-Ga-Te]

800-1100~.

followed

consistent

The

with

Halides

range

HCl,

are monoclinic

are present,

distances

type

is

(2.440(3)a).323

equilibria

temperature

ions atoms.

of the

structural

ionic radii have II CsM GaF6, where

pyrochlores

Ga-Sebr

a melt

are bonded

atom

Se

Cs6Ga2Se6

crystals

Ga2Ses6-

bridging

the

from

layers:

Gallium

GaC13,

pm,

a novel

atoms

Effective

500°C

gallium, 240

The

mixtures. isolated

and

321

structure-type.

and

with

gallium

The

Cs2Ga/Ga2Se3

238

The

TlSe

P2l/c),

crystallises

conductor,

3.3.4

of the

complexes

absorption

spectroscopy

at pressures

calculations

up of gaseous complexes: 328

between

from

suggest NdGaC16,

NdC13 in the

and

GaC13

temperature

5 to 20 atmospheres. that

there

NdGa2C19,

was

Model

is a stepwise

NdGa3Cl12

build

and

NdGd4Cl15.

Ga12-MGaI4 by thermal SyStemS

Raman

analysis.

with

compounds

3.3.5

(where

M = Na,

are

Other

formed

M = Na, Ga12

K,

forms

have

systems

continuous

been

have

solid

K or Pb; with Cs 1:l and 329 with CsGaI 4'

Gallium-containing

spectra

Rb or Cs)

been

studied

solutions

(possibly)

in the

1:3

Species

obtained

for Ga2,

In2

and

T12 molecules

171

in argon

and krypton

following

matrices.

vibrational

Resonance

wavenumbers

and

progressions

gave

anharmonicities:

the

Ga2:we"

=

-1 n = 1 cm-l; In cm -1 118 cm , 0.8 cm-'; T12: 80 cm-', I WeXe 2: -1 0.5 cm . The dissociation energies of In2 and T12 were -1 -1 , 10 kcal.mol respectively recalculated as 20 kcal.mol 180

(?10%).330 Crystal Ba8Ga7,

structure Sr8Ga7

structure

3.4

and

All by

have are

the

been

cubic,

presence

triangular

clusters 331 atoms.

of alkaline-earth

carried

space

out

group

for The

P213.

of isolated

of Ga

(or Al)

atoms

inside

INDIUM

3.4.1

compounds

Crystals the

Sr8A17.

is characterised

tetrahedral cages

and

determinations

In-N,

of C121n(02CPh)py2

structure

are

a three-centre

m.o.,

site,

two

rather sites. 332

or In-Sb

orthorhombic,

(86), with In-Cl, It was suggested that

coordination occupying

In-P

is

2.25-2.302. involves

containing

2.398; the

space

In-O,

group

PnaZl;

2.25-2.28g;

indium-benzoate

(formally In<: the conventional

than

Bonds

bonding

occupying form

In-N

only

In -0 10

one

’

Cl 0

N

A single-crystal dithizonate

pi, and The

ligand other

shows

that

indium

X-ray

the

that

two

2.477(3),

the

asymmetric

crystals unit

is five-coordinate

unidentate

positions:

diffraction

and

bidentate axial

2.467(3)R.333

are

equatorial

2.372(6),

of indium(II1)

triclinic,

is a monomeric

(trigonal

(via N and

In-N,

study

( S),

S:

space

In$dz)3

bipyramidal), In-S

spanning

2.334(6)2,

molecule.

with

= 2.468(3)2) axial

and

equatorial

group

one and

equatorial In-S,

the

172 The

InSb-Tl

system

of thallium

solubility

Compounds

3.4.2

was

groups

(which

There

monoclinic

are

The

by oxygens,

2.234(16)2 Phase

to oxalate,

equilibria

following

B-Ba41n6013

infrared

Raman

It was K or

found

Rb)

ternary

that

the

are

the

In(III)-molybdate

and

la-series

Knudsen

spectrometry

of CuInS2(s) found

reaction

was

found

formation of CuInS2 mol-l 341 . In5KS8 and

forms

in the

range

monoclinic are

present,

+

with

used

to study

(12), and

the 338 (where M =

to be

630.9+26

kJ mol -1 .

was

calculated

indium

(space

Pbl

distances

space

902-1llOK.

AH02g8

for this

The

enthalpy

of

s = -221.7*13 I

group

BZ/m.

61n8Bi4Slg

G/m).

9-

equilibrium

AH02g8

are present,

group

the

6-,

S,(g)

to be,

crystals, atoms

range

of the

. ..(12)

+

bond

and

constructed.

temperature

reaction

2.428-2.749R.342

crystals

The

parameters,

complexes

In2S(g)

monoclinic

six-coordinate

was

in the

for the

(s) -+ Cu2S(s)

system.

LiIn(Mo04)2-MIn(Mo04)2

Heteropoly formed. 340

Evidence

2CuInS2

are

regions of liquid immiscibility. No 339 formed. Complex formation was studied in

vaporisation was

along

Ba21n205,

for these,

system

are

chains

BaO-In203

Lattice

obtained

is seven-

These

Ba31n206,

at

forms

with

all

mass

four

indium

distances 337 molecules.

in the

BaIn204.

the

infinite

Ba51n208,

systems

and

bond

to H20

were

Archimedean

bipyramid.

system.

were

cell

In-O

of the BaO-In203

are eutectic, compounds

and

spectra

diagram

and

forming

studied

found:

space group P6222.

atoms from four oxalato

at 2.197(4)2,

P21/c),

average

been

for

[In2(C204)3(H20)4].2H20

groups,

were

a-Ba41n6013,

equilibrium

group

the

proposed

a distorted

bonds

2.157(2)2

have

compounds

and

forming

and

Bonds

crystals,

as a pentagonal

The

been

by oxygen

complex

oxalate

direction.

or In-Te

has

hexagonal

In-O

(space

by bridging

[OOl]

four

neutral

crystals

coordinated

the

forms

are bridging),

2.351(5)%336

In-S

analysis

is eight-coordinated

antiprism.

linked

to be quasibinary, 334 was studied.

In-O,

vibrational

NH4[In(C204)2].2H20 indium

in InSb

containing

A theoretical 335 LaIn03.

The

found

with also

Distorted

In-S

Both

kJ.

four-

distances

forms In-S

2.572(6)-2.733(4)R.343

octahedra

173 Electrical were

conductivity,

measured

OS x,< 0.1)

3.4.3 The

has

of reaction

reaction

of

solid

There

disproportionation The

Y = Cl,

pressure.

The the

diagram

30-50 are

InCl

with

In3C14,

be

are

of the

mole

aqueous

evidence

AIn2X3Y,

I, can

structures 347 types,

phase

range

detected

(for

aqueous

nitrate

nitrate

for

solutions

were

heterogeneous

InC1.346

compounds Br or

with

some

The

NaCl

of solid

InCl

was

of the

quaternary

defect

(In2Te3)x(Hg3Te3)l_x

investigated. A complex series of processes 345 place. The effects of adding Cl- and In(III)

observed.

or Te;

parameters

been

to take

on the

solutions

lattice

Halides

mechanism

appears

also

in the solid 344

and

at 300K.

Indium

solutions

microhardness

where

A = Cu or Ag;

synthesised either

In/Cl

of

The

only

In2C13

and

In5C19.

temperature

and

defect

zinc blende

or

the

system

% In.

has

mixed

X = S, Se

at high

been

redetermined

valence

The

last

in

chlorides compound

crystallises

with the Cs Tl Cl9-type of structure, i.e. it III 3 32 contains isolated In Cl - anions.348 2 9 81 Br n.q.r. tensors have been determined for (NH4)21nBr5.H20-

3.5

349

THALLIUM

3.5.1

Thallium(I)

N.m.r. mixtures

spectra

Compounds have

of salts.

been

obtained for Tl+ in molten binary 205T1+ of increase in the paramagnetic

Shifts

direction

with

increased

temperature

direction

with

decreased

size

T11[C5H4PPh2] useful

reagent 351 complexes. IH n.m.r.

coordinated 0 and N,

data to

show

amino-acids

exist around

The

via

S may

foreign

CpPPh2

diamagnetic 350 cations.

and

at pH values

from

predominantly participate

It is a

Tl(OEt).

7 to

Tl-Mn

14,

Tl(1)

0, to aspartic in coordination.

while

Tl(III)

is

acid

forms anions bridged

eight-coordinate

orthorhombic are by

crystals,

tetrahedral,

coordinates

1,4-dioxan Tl+

space

while

molecules.

is a distorted

via

Tl(I)

always

N and 0. 352

TlBrq

in chains, the

that

in the

of heterobimetallic

glycine

T1(C4H802)+T1Br4 Cmc21.

from

synthesis

8-alanine

although

coordinates

of added

can be prepared in the

and

the

group

Tl+

The

cations

geometry 353 dodecahedron.

174 205

13

Tl and

C n.m.r.

spectra

to form

a 1:l complex, 354 a carbonyl group. The

cationic

hexaniobate, studied

up to ca.

Phase

36 kbar. at 13 and

No

than

45 new

propionate

Tl(I)-carboxylate The

and

spectra

carboxylates

and

their

and

Raman

acrylate

acetate

were

were not

ion was

monomeric

in the gas-phase.

The

cell

determined.

consist

Tl... S

and

by

to 359.3 Ge-S-T1

diffraction, vapour

the

Raman

been

wavenumbers

and

Evidence detected

was

where

S3N3-

of thallium-

found

for

thermal

a

analysis

while

the

observed

always

[TlX]f

Tl+.

The

rearrangement

rationalised

by using

T1iBi(E04)2,

reactions

(except

of the

transformation

(space

peaks.

the HSAB

where

E = MO orW,

component

oxides.

temperatures

were

group

and

Pmnb),

and S N - anions.363 T1SbS2 45 pi. SbS4 units are linked

group

T12P2S6

The

R = H or aliphatic

was

still

are orthorhombic

with

by

formate,

assigned. 358 ionic.

was

intensity,

gave

tungstates,

Tl . ..Sb

(3.60-3.732)

crystals ten

and

Tl...Tl

are orthorhombic,

sulphur

atoms,

forms by weak

(3.622) space

at distances

group

of from

pm.365 system

together

pressure

can be

space

1mlNl-L. Tl interacts

The

peak

and phase

cations,

(3.50-3.68@, 364

been

spectra

of thallium(I)

the M+ peak

solid-phase

crystals,

interactions.

335.0

have

recorded

greatest

also

of these

of T12S7N8

of Tl+

triclinic

as

or very weak. All of the compounds were 360 For RCOOTl, where R = PhCH2, Ph,

strongest

parameters 362

Crystals

spectra

for RCOOTl,

or PhCH=CH,

molybdates

can be prepared

from

vibrational

were

hitherto

the

halogenobenzoates

intensities 361 principle.

Unit

had

absent,

phenyl

The

*CO2

studied.

obtained

molecular

R = Ph).

detected

fractionally completely 205 dependences of Tl n.m.r. spectra

Tl + always

Double

A bind

identified

infrared

was

radical.

substituted

and the

52 kbar,

thallium(I)

of phase changes measurements. 359

for

gramicidin

site

were

number

thallium

and

transitions 356

and bond

temperature

(I) formate

Mass

Tl+

binding

38 kbar.

synthesised, analysed, 357 assigned. Infrared acetate,

that

ligand

conductivity has been measured for thallium 355 The Raman spectra of T12C03 have

spectra

fewer

show

the

T120.6Nb205.

at pressures

to ca.

with

has

been

with

studied

e.m.f.,

measurements.

by DTA

and X-ray

microhardness

Evidence

was

found

and

saturated

for 5 ternary

175

compounds: Phase

diagrams

observed were

T12Ge2S5,

for

also

T12GeS3,

were the

system

Equilibrium

regions

TlSe-Tl4GeS4-GeSe2. for T12S-SiS2

diagrams

systems

T14GeS5

and

established,

constructed

reciprocal

TlGeS2,

have

(13)36g

been and

and

and

of glass 367 Phase

determined

for

Other

formation

diagrams 368 systems.

T12Se-SiSe2

(14).370

366

Tl4GeS4.

the

ternary

thallium(I)-

HgS

+

T12Se

g

HgSe

+

T12S

. ..(13)

HgS

+

T12Te

z+

HgTe

+

T12S

. ..(14)

containing

for which

systems

phase

diagrams

have

been

studied

are:

a71

Ag-Se-Tl;"' GeSe2-T12Se, GeSe-TlSe, 374 and Se-T1 (in the range Hg-Te-Tl; The tion

solubilities from

possible

of thallium(I)

aqueous

solutions

to grow

large

High-resolution valence

bands

x = Cl,

Br

calculation

on TlCl

assignments. resolved

The

in all

TlCl-LnC13 existence

(Ln = La,

(Ln = Gd,

T1Ge13

T13Ge15.

and

The

were

temperature

The

and for

system

diffraction T1614Se,

the

the

Yb);

studied

previous of

valence

the

diagrams

where

Xa-SW band

5d Tl

level

reveal

the

T12LnC15

(Ln = La,

systems

PbBr2-TlBr

in the

compounds

were

crystals

s solutions

found:

of T13PbBr

of KC104

The

observed

and

ionic

strength

composition

of the

system

TlI-T12Se

T1PbBr3,

was

Gd)

and

iodide

or KI

increase

and T13PbBr5,

, T1Pb2Br5 2 79

and

in H20,

at 278,

298

in solubility

were

ascribed

was

formed.

The

solid

phases 381

Pb12-TlI-H20

at 25OC.

investigated

by

and metallography;

were

TlX,

and and

with

to

an

380

factor.

Solubility,

for both

halides,

were all obtainable. 5! of dissolving thallium(I)

4.OM

established

obtained

as T13SnI

increasing entropy

phase

(Ln = Gd,

Single

aqueo determined. r

318K

to

with

Gd or Yb)

were

thermodynamics

in 0.5M

agreement

following

as well

It proved 376 purity.

Yb).378

equilibria The

crystallisa-

A transition-state

field splitting 377 3 compounds.

GeI2 -TlI.

TlGeI3,

gave

were

in thallium(I)

gas phase.

their

of high

spectra

Hg-Se-T1;373 375

Se). and

studied.

ligand

of T12Ln2C17

T13LnC16 Phase

Tl Sd levels

or I, in the

been

crystals

photoelectron

and

33-100%

halides,

have

single

GeSe2-T1Se;372

Two

crystal

new

D.T.A.,

compounds,

structure

were

X-ray T151Se2

of T16C14S,

and an

176 analogue of the latter, was found,

It was based on the TlCl

structure,

in which l/5 of the Tl or Cl atoms had been regularly 382 replaced by T12S. 3.5.2

Thallium(II1)

The decomposition

Compounds of MeT1(OAc)2

in methanol,

amines, e.g. 2-, 3- or 4-picoline, mainly N-methylation. 383

dimethylaniline

A very long paper has appeared on the parameters

in the presence

13

of

etc., gave

C and 1H n.m.r.

for a wide range of mono- and di-organothallium(II1)'

derivatives.

The major factor influencing the number of R groups attached to Tl. 384 Crystal structures

of complexes

J(Tl-C) and J(Tl-H)

formed by dimethylthallium

picrate and two isomers of dicyclohexano-18-crown-6 both there are [Me2Tl(crown)]+

is

cations and picrate

show that in anions.

The

complex cations consist of linear Me2T1 units normal to the plane through the six oxygen atoms of the ligand and the thallium atom.385 T1R3(diox),

where R = 2,4,6-C6F3H2

or C6F5; diox = 1,4-dioxan,

are prepared by the reaction of T1C13 with LiR of [NBU~] [~1~4] with HBF~ addition of dioxan.

(for R = ~6"~)~ with subsequent

Dioxan can be replaced by neutral or anionic

ligands or by metal carbonylates C~MO(CO)~-,

COG-

(for R = C6F3H2) or

to give e.g.

[THRUM]-, where M =

or Mn(CO)5-.386

The ternary carbonates T1LnIC03)2, where Ln = La to Lu or y, are synthesised at 350°C by dehydration of the carbonates T1Ln(C03)2.~H20, or at 500°C by the reaction of T12(C03)2 and Ln2(C204)3.yH20 under 3000 bar C02.387 Pentachlorothallates(II1) can be prepared by crystallisation from aqueous solutions

of T1C13 and MC1 i.e. K2T1C15.2H20,

M2T1C15.H20 (M = Rb or NH4). The potassium compound forms monoclinic crystals containing dimeric T12Cllo4- anions, formed by edge-sharing octahedra. The monohydrates are orthorhombic. 388 The crystal structure of (pyH)2T1C15.Me2S0 has been determined. There is basic octahedral geometry around the Tl in 2[T1C15(Me2SO)] , with Tl-0 2.42(2)2, and Tl-Cl within the range 2.506(6)%2.636(6)% The O-coordination of the DMSO confirms spectroscopic results. 389 T1Br3(C4H802) forms monoclinic crystals, space group c2/c. Distorted planar T1Br3 units are bridged by dioxan chairs forming

177 chains parallel

to the c-axis.

thallium is trigonal-pipyramidal.

The overall coordination The Tl-0 distance

about the

is 2.543(13)&

with Tl-Br 2.498(3)-2.509(2)~.3go MTlBr4 (where M = K, Rb, Cs or NH41 are prepared by dehydration of the hydrates or by the reaction of TlBr, MBr and Br2 in closed glass tubes at 400°C. (with the Ga[GaC14]

The K+ and NH4+ salts are both orthorhombic

type of structure).3g1

The previously-suggested

space group of @u4"N][Tl14],

P21, has

been shown to be in fact P2l/n, but this leads to only slight changes in the molecular parameters. 392

178 REFERENCES 1 2 3 4 5 6

8 9 10

11 12 13 14 15 16 17 16 19

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