Gallium and indium

101

Journal of Organometallic Chemistry, 180 (19‘79) 101-109 0 Elsevier SequoiaS.A., Lausanne-- printed inTheNetherlands

GALLIUM

AND

INDIUM

ANNUAL

SURVEY

TOSHIO

TANAKA

Department Suita,

COVERING

of Applied

Osaka

565

Introduction

the

on

same

bonding,

istry)'

ences

as

103

[2] were

and

These

and

not

GaC13

and

Pnma

in

(a-2. of

the

with

placed

M')

the

four

model

by

the

49-51,

by

these

formula

tion

has

been

close

units

(2.933 suggested

to that

* T. Tanaka,

In,

and

Tl

[l] and B, Al,

have

continued

these

in the

structure,

on

Ga,

'X-Ray and

Tl'

for

the

formation

order

chem-

Crystal

In,

at

and

(in organometallic

of

In),

(N=Ga,

Gallium

J. OrpnonetaZ.

the and

and

and

of

and

with

101-103°C

56

refer-

the

Ga

react

with

NaCZCCH

Ga,

and

In,

the

basis

NNR, and

structures

analysis

was

space

in Fig.

have per-

group

the

In atom

1; a center

an apical

position

is evidently “.The of

respec-

Raman,.%

involves

seen

distance (2.899 1) 0 A) distances-

same

shorter configura-

the v(CsC)

frequency

[4]_ with

02

yields.

Annual

Ckem., 158 (1978)

Br)

occupies

(2.989

in quantitative Indium,

as

molecules

on

rjere

and

structure

bipyramid,

compound

In),

their

structure

[3].

and

the orthorhombic

The

cell.

In analogue -indium

in

of

Ga,

Infrared, although

An X-ray

In-N'

In-C4'

for EI=Al.

solvents.

trigonal

chemists

(>l=Xl,

(CH3)2 Pfl (X=Cl

discussed,

unit

The

1;) and

by Russian

(CH3)2MCZCCH3

of neighbouring

for

enthalpies,

developed

were

per

bipyramid.

Trimethylgallium 100CH3

4) applications.

it crystallizes

distorted

In-C3'

describes reactions,

and

techniques.

bond

C-C

was

organic

compounds

In derivative;

the

trigonal

survey

1978

Ga,

on

reaction

in nondonor the

based

50-51,

a slightly

the

University,

Bonding

compounds,

of

than

being

of

and

(cZH~)~A~,

yield

dimeric

clarified

for

Al,

Containing

Structure,

(mp:

spectra

been

formed

Osaka

during

patent),

a bibliography

of Compounds

mathematical

compounds are

This one

diagrams,

Elements:

references

in 40-60X

tively) 13 C IWR

Engineering,

chemistry

in 1977.*

phase

Dimethylpropynylmetal prepared

-indium

(including

III

Reactions,

from

of

published.

A detailed (CH3)3Ga

those

'Group

Structures

Synthesis,

and

2) synthesis

on

with

Molecular

Faculty

Reviews

3) analysis

Reviews

1978

Chemistry,

organogallium

rate

of 1) reviews,

YEAR

(Japan)

and

Studies

about

THE

211.

Survey

to give

dimethylmetal

Thermolysis

Covering

the

of

Year

peroxides, the

Ga

1977,

peros-

3'

102

Fig-

ide

in nonane

OCH3

(II%),

at 120°c

Similar

obtained

The

were

by

[5]. (R=CH3

of these compounds a

or

b

exist

have

The

(50%),

and

suggested

that

probably

dimethylaluminum

(4.6%),

on the

C2H5,

as dimers

ring,

(CH3)2GaOH

and

and

yields

the M2N4C2 with

C2h

-gallium

R=CH3,

were

CH3],. that

they

tallize structure of Ga-N

studied

assume

R=CH3

and

and

skeletons

are

symmetry,

and

with

the

Raman

formula spectra

centrosymmetric

as depicted

derivatives,

their

in Fig.

2,

[(CH3)2M(NCH3)2C-

crystallographic

the

group

was

ring

analysis,

(a in Fig.

form

space

Ga compound

within

of

or C2H5.

a chair-like

the

N-C

configurations

by X-ray

in the monoclinic for

with

of were

b

Possible

or In;

Ga,

also

M=In)

compounds

a 2.

In),

(CH3)3COOH,

Ga;

CH30H

0CH3

CH3

Fig.

and

or properties

Infrared

in solution.

(CH3)2Ga-

(64X),

(M=Ga,

(CH3)3Mwith

M=Al

(25%),

CH4

structure

(CH3)2MOOC(CH3)3

HN(CH3)C(=NCH3)CH3.

eight-membered [6]_

CH3GaO

solvolysi -s of

the

of R3M

which

(CH3)*InCECCH3

(CH3)2G20(CH2)gCH3

peroxides,

N,N'-dimethylacetamidine,

packered

gave

examined

reaction

R2M(NCH3)#CH3,

3 hr

of

is no description

t-butyl

quantitatively

thermolyses

structure

(II%),

there

However,

(63%). CHSGaO.

for

CH3Ga(OCH3)2

1.

P2l/c

refined

are

1.979

2). [7]; both

with

two

1.335

The d,

has

the

dimers

to R=0.056. and

which

per

demonstrated

compounds unit

mean

respectively.

crys-

cell.

bond

The

lengths The

exo-

103

cyclic

mean

bond

lengths The

respectively. only

N-C,

of Ga-C,

Ga atom

is

and

C-C

tetrahedrally

are

1.998,

1.484,

coordinated

and

1.507

i,

distortion

is

slight. Trimethylgallium

merit

also

reacts

with

N,N'-dimethyloxamide

N,N'-bis
were

characterized

rations

with

by X-ray

respect

to the

crystal

analysis

central

oxamide

OC-NHR @H3)3Ga

+

to afford

complexes as adopting C-C

bond,

cis

as

shown

H3C>Ga/N,CA

CH

H3C\

/

H3C=

3

ratio

assigned

in detail,

and

I \o&.N/

\CH3

two

more

analysis

linked persist

[9J.

the Al

the

analogue;

proceeds

via

an

the

initial

in

(3).

(CH3)2GaBH4 order intra-

of

at

3 hr

and

Ga-N

reaction

+

frequency

The

latter

Referencesp.108

are

known

to react

was

(3)

characterized

as well

gaseous

state with

a structure,

is consistent four

is thermally

much

of ea.

less

10 mmHg

process

compounds

containing

a

Ga

appears

sense

The

exchange

with

coordinate

however, in the

temperature.

by

as elemental

polarization

with

was

(2)

to

[(CH3)2Ga]C-

stable

than

decomposes decomposition shown

1.

Trialkylgalliums

'[B].

the

LiCl

f

symmetry

intermolecular

by

+(CH3BH2)2

the

a pressure

were regions

synthesized

C2u

at room

condi-

also

at -15“C.

obtained

Such

increasing

the

isomers

was

tr bF!R spectra,

tetrahydroborate

gaseous of

and

l°C)

of a solvent

having

group

on

&pans

Ga-0, ca.

compound

and

spectrum

phase,

Dimethylgallium

a half-life

Scheme

BH4

and

(CH3)2GaBH4

The

(CH3)3Ga(u-H)2BH2

condensed

Ga-C, (mp:

--)

infrared,

infrared

cis

(CH3)2GaBH4

-

method.

mass,

to a bidentate in

the

is dependent

the

absence

LiBH4

+

The

model

[BH41--

with

B2H6

satisfactory

.molecular

of

in

in the

+

weight,

formed

spectra

tetrahydroborate

(CH3)2GaC1

molecular

of isomers

Raman

reactions

(CH3)3Ga

k

especially

Dimethplgallium following

(1)

\Ga__vCH3

.C

k

The

2, re-

,,N

_Ga

GaLCH

\o,,c.N/

Infrared

1 and

3

0

_CH3

I

I

tions.

in

which configu-

P /O

spectively.

1),

trans

iso-

(CH3)2Ga(RN-COCO-NR)Ga(CH3)2

-

R I

H3C=

(Eq. and

two

-2CH4

I OC_NHR

R=H.

the

and

the

'active

in

104

Scheme

1

H3C\

H,c\Ga/.H--.B/H _ HC' 3

/-H-m_ , CH3 R\ H

HHGa\RY

\H"H

H, -

/H.__

,CH3 B\

HHGaLHd

CH

3

3

hydrogen',

eliminating

compounds

[e.g.

frequently

occur

were-obtained

by

see

alkane

K.

to yield

S. Chong

et al.,

as dimers.

Thus,

the

of R3Ga

reaction

either Can.

four-

or

five-coordinate

J_ Chem., 55 (1977)

L-prolinatodimethylC2H5)

(R=CH3.

and with

gallium

25401.

which

-diethylgallium

L-proline

(4)

in refluxing

Oy/OIGalfyR \ I -N---H

H---C

HC 2

I

\

\

C

/CH2

H2 4 benzene space

[lo]. group

The

P212121

dimethylgallium with

Z=4.

derivative The

crystal

crystallizes structure

in

consists

the

orthorhombic

of molecules

0 C 0

Fig.

3.

The

dimethylgallium

each bonds

of which to form

is linked

to two

a chain-lfke

unique

part

of

the L-prolinato-

structure.

others

polymeric

by weak structure.

Ga-0

bonds As

and

N-H-O

illustrated

hydrogen in Fig.

3,

the

105 Ga atom

is five

Important and

bond

Ga-C,

(cH3)3~ ylide

coordinate lengths

l-924(5) (M=Al,

and

Ga,

dimethylmetal

and

are:

has

l-958(5)

In,

distorted

Ga-O(axial),

Tl)

2.

react

complexes

trigonal

2.044(3)

It also with

shown

bipyramidal

and

was

2.k95(3);

repprted

geometry. Ga-N,

in a patent

(CH,),P=NP(=CH,)(CH,>2

to give

2.035(3); [ll]

that

'double

in 5.

(H3EQ2 /

\

I

N

\;_C/M(CH3)2

(H3C12 5:

Xethylgallium

Hp

M=Al,

Ga,

In,

Tl

diacetate,

CH Ga(OOCCH >was prepared by the reaction of 3 3 2' (CH ) Ga with CH COOH in a l/2 mole ratio. The structure was determined by 33 3 vibrational spectroscopy and X-ray analysis 1123. The methylgallium compound crystallizes

in the

unit

The

cell.

meric

Beside

coordinated

depicted the

monomers

layers.

groups

monoclinic

at

in Fig.

acetate

4;

groups

are

space linked

the

distorted

Ga(2)

bonded

atom

to Ga(2)

P21/c

together

the bridging the

group

with

by

acetate

acetate,

there

trigonal

bipyramidal

is coordinated are

all

eight

are

formula

groups, also

&its

forming

'free'

poly-

acetate

coordinated

distorted

per

Ga(l),

tetrahedrally

as and

bridging.

0

C

Fig.

Methylgallium tetrahydrofuran

acts of

as

the

to

yield

Referencesp.106

MN6 Its

core-

structure

reacted

sodium

ligand

[CH3Ga(N2C3H3)3]2M

complexes.

The

dichloride

a tridentate

an octahedral

4.

with

The

coordination

sodium

pyrazolide,

Nat(N2C3H3)-,

methyltris(l-pyrazolyl)gallate

to bivalent type

of CH3Ga(OOCCH3)2

(H=Mn, ligand ability

transition Fe,

forms

Co, also

in MO.

W,

Ni,

metal Cu,

ions, Zn),

a variety and

Hn

(6).

This

giving

cpmplexes

which

may

of metal

carbonyl

in

anion

possess

carbonyl

derivatives

was

107 conditions_

In all

In the

however,

the

the

X+[M(CH3)4]-

force

(M=Al,

and

the

using

and

of alkyl can

of

than

M=Ga,

for

in

tetrahydrofuran, reaction.

?mlH4.

compounds

P(CH,$4;

procedure

in gas

(C2H5)3N

IV to VII

of

the

Group

III

M=In,

X=AS(CH~)~;

Thus,

elements, X=Na.

a set

As-

of comparable

Si,

P/Ga,

Ge,

of

force

constants

determination

of

by

on a surface

chromatography

(M=B,

elements

derivatives

thermal

or

to the metalation

As/In,

Sn,

Sb

[15].

Diagrams

volumes

be minimized

film

active

tetramethyl

and

a new

Phase

points

Group

X=K

less

in diglyme

in preference

) ), have been assigned in detail. 34 for the tetramethyl compounds of Al,

Retention boiling

are

of

system

proceeds

Sb(CH

obtained

Analysis

MGaH4

spectra

constants

were

reaction

reactions,

Vibrational

(CH3)4,

NaGaH4-HC3X6H5

addition

Group

H20-

decomposition

of

It also III

and

chromaton

In,

Ga,

1161.

the

using

of

Al,

02 -free

products

given

Tl)

reported

during

He

as

as well

was

elements

N support

the

were

of

gas

The

Cr

the

as ethyl

compounds

that

decomposition

the

chromatographic

carrier

[17].

functions

and

film

by

of

analysis

depositing

was

a Cr

deposited

of bis(ethylbenzene)chromium

by

synthesis

at

350-400°C.

tial

A phase

diagram

thermal

analysis

of

the

(CH3)3Ga-(C2H5)3As

_ The system

[18].

pound

of an equimolar

composition.

curve

corresponding

to

ation

in the

state.

liquid

the

system

contains

A smoothed

chemical

compound

was

one

by

congruently

maximum

has

obtained

melting

observed

indicated

its

differen-

on

the

partial

comliquidus

dissoci-

Applications Several (M=Ga,

In,

evaluated

organometal(II1) or Tl;

in vi&o

or CH2C6H5;

against

five

has

the best

(C6H5)2GaS2CN(C._,H,_)2 Epitaxial arsenide for

are

developed

by

mixtures and flow

The

rate,

pressure

torr, AsH3

in several

thus

and

obtained

from

and

were

On

the

other

(CH ) Ga and 33

by

ASH

hand, 3

crystal with

AsH3

partial

For

1201. the

GaAs

given film

of

the

film

measurements, kinetics 2

these,

carrier

of

the

crystal

a new

gallium

technique

Si or Ge was

pressures, values

also

studies, and

test

chemical

gas was

studied

rate of

were

25-76

of -J, H2

growth

Effects

crystallographic

in a H

2) were

Of

(CH~)~G~-ASH~-F~

concentration.

Hall-effect

or

single

Thus,

single

H2 and

growth

Rn?f(S2CNR'2)3_n

[19].

1-1,of

process

temperature,

on

n=l

activity.

on

flow

torr;

evaluated and

bacteria

applications. films

(CH3)3Ga

temperature

formula

of CO.2

at 520-750°C

increasing

photoluminescence

of GaAs

40-100

concentration.

devices.

device

deposition

(P),

four

thickness

ultrathin

respectively)

with

and

the

or aryl;

antimicrobial

microwave

vapor

of

R'=alkyl

fungi

as with

of such

a.chemical

concentratiqns films

such for

growth

linearly

analyses,

tion

useful

(total

0.5-2.0

creased AsH3

films,

epitaxial

dithiocarbamates

R=C6H5

the

inH2

and

examined_ impurity performance

vapor and

deposia mass

108 transport

model

for

the

reactor

comparison

of experimental

Korphclogy

of GaAs

was

reported

has

data

epitaxial

been

with

layers

presented

kinetic grown

to serve

models

in the

for

the

as a basis growth

for

process

(CH3)3Ga-AsH3-H2

system

[Zl]. also

[223_

References 1. 2.

OrganometaZ. Chem., 6 (1976)

J. ?. Maher,

(Pub.

1978).

KoZ. S&rue&. ~.fj%. .Vethods, 5 (1977) 382;

M. B. Hursthouse,

88

78

Chem. Abstr.,

(1978) 180350n.

3_

K_ K_ Fukin,

4_

W_ Pries,

5.

Yu.

Kut'in,

Chem. Abstr., 88

2410;

W_

159 (1978) A.

V.

A. H_

and

I_ A.

(1978)

Frolov,

I&him., 47

(1977)

50110~.

H_ D. Hausen,

Schwarz,

232. Obstih.

and

J. Weidlein,

J.

Chem.,

Or,canome~aZ.

373.

Aleksandrov,

N. V. Chikinova,

G. I. Xakin,

Zh. Obshciz. Khim., 48

I. Bregadze,

(1978)

N. V. Kornilova,

and

Chem. Abstr., 89 (1978)

467;

6352a_ 6.

F. Gerstner

7.

H.

and

8.

P. Fischer,

R. Graf,

9.

A_ J.

and

D. Hausen,

J. Weidlein,

F. Gerstner,

Z_ Natirforsch., and

W.

Schwarz,

338

(1978)

24.

OrgazzmetaZ. Chem., 145

J_

(1978) 277.

10.

Downs

K. R. Breakell, (i977)

11_

H.

and

J. Organo.metaZ. Chem.,

J. Weidlein,

P. D. P. Thomas,

J. &em.

S_ J. Rettig,

Starr,

A_

Sue., DaZton, and

J. Trotter,

144 (1978) 95.

(1978) Ccm.

809.

J.

Chem.,

55

4174_

Schmidbaur

and

H. J.

Fueller,

Ger.

O_f:ceen., (1978)

Chem.

2,701,143;

Abstr., 90 (1979) 23243d. 12_

H.

D. Hausen,

160 (1978) 13.

K. R. Breakell, Ccn.

14.

V. V.

V.

Xhim., 48 H.

16_

I. Tohyama

and

17,

A.

D. Zorin,

J. Meidlein,

Rettig,

and

D. L.

44

E. B.

Sokolov,

Ferapontov,

S. Kolesov,

(1978)

Schrem,

2067;

and

W.

Schwarz,

Singbell,

22;

C&zm.

J.

OqarzzmetaZ. Cham.,

A.

Starr,

and

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V. A.

Smirnov,

and

I. Zakharkin,

L.

Zh.

Chem. Abstr., 90 (1979) 38983u. Spectrochim. Acta, 34A 288 (1977)

V. A. Unilin,

and

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549.

286.

N. El. Sorokina,

Zavod.

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B. K. Skachkov,

and

N.

2. A-zaZ_ Chem.,

K. Otozai,

(1978)

Yu.

3. Weidlein,

V. K. Vanchagova,

Lab-,

88

S. J.

Gavrilenko,

G. Tatzel,

18.

Sille,

J. Ctiem., 56 (1978) 2099.

Obskh. 15.

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411.

Fedorov,

E. A. Zh.

Efremov,

Fia.

B.

%%m.,

52

I. Kozyrkin, (1978)

A. P.

798; Chem. Abstr.

(1978) 198544p.

19.

T. N.

Srivastava,

20.

J. P. Duchemin,

V. Kumar,

(India), 1 (1978)

685;

M.

97;

Chem.

Bonnet,

and

0.

P.

Srivastava,

Abstr., 89 (1978) and

D. Huyghe,

Chem. Abstr., 89 (1978) 14874n.

Rev.

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141068~. Tech.

Z'homson-CSF,

9 (1977)

109 21.

A. L_ Lin, (Proc.

V. Dao,

Intl.

Conf.

and

L.

Chem.

F. Donaghey, Vap.

Proc.

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EZe&rochem. Sot., 77 (1977)

6th)

264;

Chem. Abstr., 89 (1978)

515&b.

22.

L. S.

Ivanov,

B. P_ V.

Baronenkova,

N. Karpukhin,

N. Nauch.

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V. M.

N--i_ i P&ekt.

Lenivova,

and

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Timashkov,

N. G.

In-t Eedkomet.