Bismuth

143

JoumatofOrganometattic Chemistry,180(1979)143-151 O~evierSequoiaS.A_,Lausanne-_~dinTheNetherlands

BISMUTH ANNUAL SURVEY G.

0.

OOAK

COVERING

AND

LEON

Department of Jloorth Carolina

An 1977

German of

the

of

thesis

has

organic (out

been

of a total

sive

subject

article

also

are

626)

text

are

the

to transition and

article

to transition

elements

compounds

described

This

review,

bismin

article in the

however,

(bismabenzene)

V heterobenzenes mentioned phosphorus,

not

has

been

[7].

One

article

arsenic,

antimony,

Bismuth;

Annual-Surve.y (1978)

also

arsines, value.

discussed

until

in a review

on six-membered

the year

organobismuth

of organo-

and

their

in this and

the The

use

review.

A

bisnuthines

in

compounds and

were

-bismuth

year

1976

chemistry

article

C.61. of

on Group

compound

heterocycles

in a [S] have

chemistry

-antimony during

in the

the _?&.%--0t?urar

in which

discussed

157.3.

pages

a comprehen-

authors

heterocyclic

or bismuth

of

organobismuth

literature

published

and

same

stibines,

A few

to

Thirty-six

were

discussed

syn-

discussed

compounds

on organoarsenic,

covering

p. 141-150.

been

coordination

organobismuth

in a review

Vol.

163

were

chemical

was

the

These

organobismuth

psosphines,

of considerable

elements

monograph,

of organobismuth

is an author

Compounds

Levason. on

as

in a review

[3].

properties

above

is devoted [2].

synthesis

revision

a review

mentioned

the

there

body

of organic

matter

bismuth

recent

in

Techr.oiogy

coordinated

was

and

have

compounds

of organic

to

on methods

subject

'The

physical

to the

compounds

of some

review

series

in both

index.

and

Organobisrxth

synthesis

this

synthesis

in late

by Chemiicaz

of Contents

In addition

the

appeared

no author

and

The

comparison

the

devoted

stibines. ligands

but

antimony,

[4] by YcAuliffe

published

compounds

XaZeigh,

as abstracted

is in German,

OF ChznizaZ

book

covers

compounds.

in which

on bismuth

compounds recent

and

of arsenic, of

ihziversity,

is a Table

index

published

index.

EneycZopedia

There

Houben-Weyl

The

State

literature

familiar

compounds

compounds.

1976.

organobismuth the

the

a formula

is in German

known

a volume

of

and

CazzoZina

on organobismuth

covers

Xay

English

text

of all

volume

through

and

FREEDMAN

monograph

This

Absk-sets

D.

Chemistry, North 27650 (U.S.4.1

important

111.

THE YEAR 1978

was

containing

[S].

1977

see

J. Organometal.

P&em..'

-

144

Weber the

type

and

Baudis

R2BiOR'

.Ph,BiOR,

was

where

The

compounds

ulak

CRXe,, was

from

thiols CNeS,

obtained

mass

which

weighta(from

were

the

compounds

compounds

-The solvent ROS.

The

for

the

compound

compounds

not

could

evaporation

of the

melting'when than

alcohols

cryoscopic in nature. determination

of

+

EtOH

from

(where

by

elenental

where

+

of

Et,

the

molecreact-

prepared

from

PMR,

molecu-

in each was at

All

t

case

obtained

low

and

however,

their

PIR

compounds

i-

the

were

of

that

but

the

obtained

3BSR'

-f

their

2, CXeS,

'gHIS

form

by retwo by

without

solvents

other

weights

by

were

polymeric

in CDClB

to allow

as

follows:

+

2ROH

or o-C6H4Xe)

alcohol,

other

molecular

compounds

soluble

PIeBi
The

as powders

in organic

the

thiols

of

decomposed

spectra. with

preparation described.

corresponding

in crystalline

sufficiently

reacted

R' = CWe

was

solubility

suggested

the

2XaBr

compounds

the determination

It was

and

reaction:

temperatures,

three

slight

[lo]

or CIfXe2, was

following

YeBi(OR),

be crystallized

Their

analyses,

laboratory

R = Xe,

by means

solvent.

2

and

compounds

data).

Mieber's

were,

Xe3i (OR)

The

easily

Ph2BiSR

prevented

The alkoxy

were

*

ethanol

methods. They

compounds

to atmospheric

Ph BiSR, where R was 2 Another compound prepared

RSY

2SaOR

heated.

type

NaBr

XeBi(OEt)2

from

the

compounds

PPlR data

reported-.

+

reaction

crystallization

sensitive Both

C6RkF!e-p.

thio

spectral

f

were

of

four

of

NaBr

crystals,

data

compound

reaction:

Ph2BiOEt

obtained

2

+

known

prepared

the

*

paper

P!eBiBr

now by

NaOEt

?feBi(OR),,

were

only

membranes.

characterized

mass

the

isolated:

C

In a second

fine

The

+

Ph23iOEt

lar

as

compounds

not

Ph2BiBr

compounds

Ph2BiOR

(cyclohexyI),or

was

The

+

spectral

to yield

C6Hll

have

or Ph,

to mucous

Ph2BiS(CH2)3SBiPh2_

Ph2BiOEt

They

CBXe2,

NaOR

irritating

weights

ed with

f

were

and

Et,

that

noted

Et2BiOEt.

R = Ne,

Ph2BiBr

moisture

[9] have

145 It was

not

MeBiBr2 sodium

on

HeBi(OR)2 ing

to

were

and

add

soluble

the

basis

reacted

to the

The

l%R

alkoxy

of

in organic

solvents,

and,

but

after

the mercaptan.

spectral

freshly

compound

in alcohol

a solution

of mass

with

the

(NaOMe)

distilled

The

could

data

were

CS2

simply

be

of

thio

readily

the

compounds crystalliz-

monomeric.

to give

to react

removal

The

alkoxides

xanthates

accord-

equation:

NeBi(OR)

spectra

xanthates

to isolate

an alkoxide

bronide,

NeBi
necessary

with

+

2

of

2cs2

*-

the methyl

appeared

at lower

XeBi(SC(S)OR),

protons field

the methyl

signal

of compounds

attributed

to a five-coordinate

attached

to bismuth

(approximately

of

the

type

bismuth

0.5

in

ppm)

XeBi(SR),.

the

than

This

with

result

was

structure:

Roc~S~~~/s\COR \,/ \// S

Mass

spectral

data

on

the mercaptides

for

the monomeric

form,

not

be obtained.

The

authors

the

alkoxy

spectral

been

data

A number

of

reported

by Bochkarev

continuation the

for

type

[(C6F5)3N],M',

At

as

reaction

compounds

containing

studies

from

Nwas

[II].

this

Si,

f

at

170°C

gave

the

third

ethyl

All

temperatures.

EtBBi

out

attempts

metallic

bismuth

was

be

Referencesp.150

isolated

and

bond

have

is a

on compounds

or Sn and

?l' was

reacted

[(C,F,),Ge]BiEt2

absence

with

also

reacted

Ge compound, in pure

The

form.

authors

only

of

either

_a

triethyl-

of

the

with but

EtH

were

by an

under

product

same

unable

to

Bi at higher exchange

unsuccessful.

reaction

EtBBi

the

The

were

metallic

[(C6F5)3Ge]3Bi

(C6F5)_,GeBr

as one

f

of a solvent.

obtained

to obtain and

obtained

(C6F5)3SnH

corresponding

-f

in the

group

(Et3Ge)3Bi

not

Bi-Ge paper

laboratory

Ge,

[(C6F5)3Ge]2BiEt.

between

the

the This

mass

follows:

carried

compound

useable

element.

reaction

could

to obtain

XeBi(OR)2.

coworkers

where

was

reaction

tin

unable

90-100°C~tris(pentafluorophenyl)germane

(C6F5)BGeB

than

were

gave the molecular ion 2 for the xanthates could

ion

compounds

and

or a main-group

bismuthine

replace

NeBi(SR)

the molecular

interesting

of previous

transition

The

but

Again

products.

The

milder

conditions

was

unstable

and

.

146 The slow was

reaction

heating

of

in the

evolved


as ethane,

teSlperatures_

Rapid

but

two

heating

reaction

in which

product

obtained

in both-cases

[(CgF5)2GeBiEt]2. after

This

recrystallization

compound

one mole

was

of ethane

was

liquid,

not

The

be purified

of the

compound

(C6F5)2Ge(R)BiEt2

reaction

mixture.

(C6F5)2GeH2

the

f

The

obtained

was

suggested

three

stability

of

was

surprising

to completion the

two

Et3Bi

the

stability

corresponding Tt was

-f

the

Ge-Bi

bond

reactions.

the

the

same

reaction

the

would

reaction

3[(C6F5)3Ge]2BiEt

Bi-Ge

[(C6F5)2Ge(H)BiEt2]

IR was

-a

(C6F5)~Ge=":~e(C~F5)~

the

was

bond

cleavage

cleaved

by BrL? and

[(C6F5)2CeBiEt]2

The

required

presence

of

by Xl,

bond

as

of

display

the

high

carried

3Hg

[(C

+

out

but

to HC.1 cleavage three the

days

C6F5

to go

group

in

[(C F ) Ge12BiEt does not increase 653 indicated by a comparison with the

compounds.

conditions

f

order:

and

authors

that

reactivity

(C6F5)3GeBiEt2

was

was

reaction

tenjerature..

Ge-Bi

in the

compound

expectation

However,

when

compounds

(C6F5)3GeBiEtz

phenyl the

the

scheme

of

I Et

the dimeric

at room

of

the

I

the new

in that

compounds

by

loss

but

Bi

compounds

the

the

reaction

.I

In all

of

by

characterized,

(C6F5)2Ge=BiEt

of

crystalline

results:

-+

stability

compound

to be a polymer

following

a

The

formula

to the

(C6F5)2G%ByEt

The

in

evolved.

the

On group

at higher

resulted

crystalline

and

of the

for

with

ethyl

cleaved

were

material

presence

to account

one

In addition

spectrum suggested

complicated.

only

were

orange

believed

obtained.

could

a dimer

benzene.

more

however,

of ethane

a bright

from

an undistillable

[(C6F5)2GeBiEt]2,

groups

60-10S°C,

two moles

was

was

60-105°C,

ethyl

at

violent

Et3Bi

range

did at

not

20°C

F ) Gel2BiEt 653

compounds

in transmetallation react

for

six

reacted

3t(C6E5)3Ge12Bg

containing

+

with days. as

2Bi

metallic Under

follows:

-I- BiEt3

Iig the

147 In an

investigation of

and

[12]

attempted

ICN.

Instead

they

largely

devoted

Singh

Ph3Bi

and

the

In a paper and

stibines,

be readily argon. out

room

Ph3BiF2.

Ph3Bi

authors

were

sulfur unable

had

II of

proceeded

Cl41

salts

in the

which

following

Ne

References

>

p. 150

and

of the

that

the

presence the

were

was

f

was

reported

can with

carried

for

phosphorus

the

reaction

stibonium

as

between at

ylids,

PhSSb

200°C.

or

The

or bismuthonium

to isolate evidence

and

sulfonium

of NaBPh4

able

taken

manner:

Ph3Bi diluted

reaction

trivalent

studied

they

arsines

78%.

that

either

between

tertiary

fluorine

l3 C !i?lRwere

Xe

Ha.

reported

triaryl

Bhattacharya

reaction

of

xe [NeBiPh3]BPh4

the

carbonyl-stabilized

NaBPh4 >

by

Bi,

fluorination

was

I in the

However,

these

or

Phi.

in CFC13,

have

of mixed

Sb,

and

have

1'F'and

reaction

to isolate

tetraphenylborates. product

1131

dealkylate

ylid

Ph2BiCN

by a stream

demonstrated

will

coworkers

the

Bastian

Both

in the

As,

Ph3Bi(CN)I

to the

dissolved

preparation

E was

isolated

to Ph3BiF2

was

yield

to the

where

to prepare

and

previously

and and

3

EXY,

temperature'.

compounds

Arbuzov Ph3Bi

Ruppert

The

Having arsenic

Ar

fluorinated

The

at

type

devoted

compounds

the that

cleavage the

reaction

148 The

2-phenylthiodimedone

of an authentic The As,

Sb,

of a Group to

of the

or Bi, has

Group

studied

little but

not

the

the

rate

of hydrogenation

was

dependent

on

butenes

however,

or Ph3Bi

as judged

More

isoprene

The

was

formed

Ph3P

P-methylbutane

the

was

spectra or Pb)

independent

there

Ph3As

and

the

Group

the

metallic

compounds

was

then

obtained

and

unfreezing. during

oxygen.

These

complex

between was

Sb,

The

in n-hexane after There

was

procedure were

which

of this constant

V2lues

or Bi, were Ph3S

Rq was

to Ph3P

results coaplex,

were and

given and

and then

cerned

for were

between

interaction

was

the

absent

P 5 :\s > Sb 5- Ci.

found

phenyl where

(C, Si,

on

emission Ge,

Sn,

to obtain

between

spectra

in the

reversed

of

the

of

intensity

by

and

oxygen the

organo-

the

addition

of

The

of a

bimolecular

equation:

Kq[021

quenching

constant)

Ph3P

of an electron

o rings

of

formation

oxygen.

Pb E where 3' to decrease markedly

was

the

reversible

slo.*ly between

in K

IV

compound

in terms

the variation

+

the

the

increase

interpreted

interaction

1

Ph3Sb

site

used.

77 K in order

Stem-Volmer

Ipun = (where

was

compound

the

with

active

electronic

of conplexes

increase

indicative

organonetallic to obey

Ph3Sb

formed_

poisoned the

V poisons

Luninescence

Z-methyl-

either

first obtained at 77 K; the spectrum -4 torr and alternate freezing

a marked

this

found

at

but cata-

at 10

evacuation

results the

were

little

butenes

of

of Group

or Bi)

pressure

than

was

the

of Ph3E

unpoisoned

various

Group

the hydrogen

presence

selective

studied

properties

species.

upon

hydrogen

catalyst

of

absence

by Pd-on-carbon

As with

the nature

have

E = P,

2-methyl-2-butene

comparatively

derivatives

(N, P, As,

organonetallic

quenching

[16]

of phenyl

V

reduced

the

the

where

In the

In the

mote

between

forzned when

on donor-accepror

spectrum

point

hydrogenation

depended

of

was

were

ratios

coworkers

of a number

information and

and

Ph3E,

and

concentration.

and

and

by

was

rate

or Ph Bi. The authors suggested that 3 the catalyst varied with the different Razuvaev

the melting

[lS].

concentration.

isoprene

were

butane.

Bailar

3-methyl-1-butene,

isoprene

the

compounds

and

2-methylbutane.

pressure

lysts,

to depress

of palladium-on-carbon by Fujii

V triphenyl.conpound,

very

not

V triphenyl

on poisoning

been

forrt Z-methyl-l-butene,

with

found

sample.

effect

isoprene

II was

attributed and

E = N and

the

in going

from

Ph3Bi.

These

and

donor-electron to the

elenent

decreased

E = N, P, As,

amount

E.

markedly

Thus

Sb,

acceptor of rr'-3 r-r such

in the

sequence

149

The (where

photoinduced

E = As

compounds group)

(DV)

or Sb and

and

[Et4N][V(C0)6]

has

been

studied

[Et4?J][V(CD)6]

the

[T'I~-C~V(CO)~]

two

the

compounds

compounds

compound

the

'17

in the

given

and

shift

order

but

alcohols easily

effective

values

Et5Bi

prepared

readily

particularly applicable

useful

carbon

cleavage were

to keep

tetrachloride

of

gel

of

the

room

temperature

decomposition

in the

chlorinated

a resinous

solid,

has

to be

alcohols

was

formed

the

by

mixture

with

acetic

in solution. chloroform,

studied

or

by Razuvaev

more

In every

was

also

compounds

reaction

rapid

case

in pyridine

Ph3Bi,

PhH,

polymerization

obtained:

0

of

/I

solvent

Pb_,Bi

and

triphenylbisnuthine

been

by

was

It was and

carbonyl

to be

secondary

reagent

benzene.

somewhat

formed

ligand

found

and

in pyridine,

solvents.

believed

been

The

substances

wac

From

dichloride

or

The from

the

increasing

has

triphenylbismuth

separated

of

ligands.

given.

[l&I].

of allylic

with

v ,XXR spectra

values R3P

of primary

chloroform,

bismuth-containing

than

were

oxidation

but

51

and

spectral

respectively

or by heating

The

benzync,

cis-

of overall

of pentaphenylbismuth at

obtained

and

corresponding

1,2-giycols.

1191.

coworkers

the

oxidation

readily

the

deconposition

solution and

the

on silica

in order The

for

ketones,

St,,Bi and

was

< R De< R Sb was 3 3 dichloride,(Ph5BiCl)gO,

hydrolysis

for

reactions

chromatography

end

the

with

ER3

in the

cyclopentadienyl

IR spectra

a sequence

in dichloromethane,

to the

in these

acid

by

soluble

and

the

ligands

EtjBi

With

< R5As

reagent

to aldehydes

compared

with

Oxybis(triphenylbismnuth) a mild

]173.

The

the

and

= the

Rehder

isolated.

obtained

h?fR chemical

strengths

and

by

ethoxy)

[n5-CpV(CO>3BiEt_,]

were

were

or

[Et4X][V(CO)5BiEt,]

compounds,

previously

of CO groups

aryl,

[n5-CpV(CO)4]'(Cp

by Talay

I~5-CpV(CO),(BiEt3)zl, of

substitution

R = alkyl,

>

Ph5Bi

+

?hH

f

II

\

The

formation

presence

of

Diels-Alder ed,

while

ether. in the was

of benzyne furan, addition

with

!&en

presence

believed

p.

150

product pyridine

decomposition of Ph3Sb,

demonstrated

alcohol, was

by

isolated,

the

/ II + 0

products

of Ph5Bi

antimony

PhgSb

running

or moist

was

an organoantimony

to be a dipolar

\

References

moist

the

was

t-butyl

with

%BuOH,

included

reaction

in the

!Flith THP , the t-BuOPh

phenol

and

was

obtain-

diphenyl

carried

out

in Ccl4

solution

product

was

obtained

which

compound

*

the

pyridine.

(see Antimony

section):

150 The

authors

postulated

solvent to give decomposition

the

that

to yield

bismuth

compound

decomposed which

in an organic

then

underwent

further

benzyne:

solvent

Ph5Bi

Pb3ii

pentaphenylbismuth

dipolar

>

Ph3zi

--0 1

/ 0

,

,

-0

1

+

Ph3Bi

C

+

PhH

II

\

-REFERENCES

1

H. Wieber,

2

Verbin&ngen,

Chemie, Bd. 47,

Springer-Verlag,

Berlin,

1977.

S. samaan, fifethodender orgaaischen Chemie (Houben-:JeyeyZI Bd. &fetaZZorganische Verbindungen, As, Sb, Bi, Georg

13, Pt-8: Thieme 3

der Anorganischen

&&buch

GmeZin

Bism&-Organische

Verlag,

G. G. Long,

Stuttgart,

1978,

L. D. Freedman,

pp.

590-626..

G. 0. Doak,

and

Xirk-Othmer Eneycz.

Chem. TeehzoZ.,3rd Ed., 3 (1978) 921. 4

C. A. McAuliffe

and

Phoqhine,

W. Lavason,

Arsine and Stibine

CompZexes 0,' the T'rcmsition Elements, Elsevi_er, Both for

Chem. Abstr., 89 (1978) this

book

W. Levason

indicated

and

2??? .?A, VGl.

-Amsterdam,

various

publication

1979.

advertisements

date

was

1978.

P.cc. Chem. !?es., 11 (1978)

ilcc. C'hem. x?es., 11

363.

162.

(1978)

153.

ed. .?odd's Chemistry of Carbon Compounds,

in S. Coffey, iv,

and

Chem., 6 (1978)

Orgcnomet.

III,

R. E. Atkinson

a SingZ~

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