Decarboxylation syntheses of some polyfluorophenyl -tin and -germanium compounds

DECARBO&TION

SYNTHESES OF SOME L’OLYFLUOROPHENYL -TIN AND

-GERMANIUti

COMPOUNDS

G.

and G,

B. Deacon

Chemistry

’

f. Farquharson

Department,

Monash

University,

Clayton,

Victoria

3168

(Australia) (Received

April

26th,

1977)

Summary The triphenyltin R-EtOC6F,,

_

carbcxylates,

or o-HC6F4)

~-(ph,Sn02C)2C6F4. hydroxide

in boiling

triphenyltin

compounds

owing to competing

Ph3Sn-R-HC6F4,

polyfiuorocarboxylic

of Ph3Sn02CR

(R = C6F3,

For R = R-MeOC6F4,

gave B-(Ph3Sn)2C6Fq

whflst g- (Ph3Sn02C) 2C6F,

PhgSnOZC-g-HC6f4

failed to react.

and tetrafluorophthalate

pyridine giving R-(PhHg)2C6F4 B-(Ph3Pb02C)2C6F4

acids

ga-ve triphenyltin

underwent decarboxylation

pyridine gave pentafiuorophenyltriphenylgermane,

with silver

with silver g-ethoxytetrafluorobenzoate

and

in boiling whilst

and tetraphenyl-

pentafluorobenzoate but analogous

and disilver

tetrafluoro-

up, mixtures of polyfluorophenylgeranes ,

and (Ph3Ge)20.

* Preliminary communication,

of

fluoride,

respectively,

Ph3Pb-p-HC6F,,

boiling

Ph4Ge,

the yield was lowered

and g-PhHgC6F4C02HgPh

gave R- (Ph3Pb)2C6F4,

after work

_wlyfluorophenyl-

Di(phenylmercuric)tetrafluorotere-

of bromotriphenylgermane

gave,

or

(major product) and

Reaction

terephthalate

in methanol.

Similar decomposition

lead.

reactions

of triphenyltin

P-MeOC6Fq,

pyridine gave the corresponding Ph3SnR.

p-MeOC6F4,

and

by reaction.

forniaticn of tetraphenyltin.

E-(Ph3Sn02C)2C6F4.H20

phthalate

have been prepared

with the appropriate

p-EtOC6F4)

(R = C6F5,

I R- (Ph3Sn02C) 2C6F4. H20,

Hz0

Thermal decomposition

Ph3Sn02CR

Ref.

[,I] .

in

74 Introduction

.

Thermal decarboxylation

synthesis

reactions.ha&

of organomerourials,

contains

electron

organometallics

[ 2-q..

withdrewing

proved very useful

particularly

substituents

[ 23 ;

compounds

tiphenyllead

been extended

to bis (polyfiuorophenyl)diphenyllead

Decarboxylation

this route [2,

pol-yfluorobenzoates, organolead

(a)

_

Polyfluoroof the

other organotin

compounds

[ 93 .

have not been

com_pounds have been obtained have been obtained

by

of polyiluorophenyl-tin

by thermal decomposition

together with some related

by

and

of the appropriate syntheses

of mercurials

and

compounds.

of Trinhenyltin

The organotin g-EtOC6F4,

or g-HC6F4),

appropriate

Analytical

i

acids

of tiphenyltin

supporking

g-methoxytetrafluorobenzoate

63 = z-MeOC6F4,

R-EtOC6F4,

and not as hydrates.

However,

H20

(1)

triphenyltin

@3OC6F4,

could be obtained analysis

was unhelpful,

(102O) _

f

(see Experimental)

(R = o-MeOC6F4,

Thermogravimetric

up to the melting-point

except

as hydrates

for hydration

or PMR spectroscopy_

anp’o-(PhgSn02G)2C6F4.

hydroxide .with the

Ph3Sn02CR

that all complexes

of Ph3Sn02CR evidence

R-MeOC6F4,

in methanol. 4

should be formulated

in the case

(R = C6F9,

R-(PhgSn02C)2C6F4.H20,

RC02H

data suggest

benzoate

Ph3Sn02CR

by reaction

carboxylic

Ph2SnOH

Polvfiuorocarboxvlates

carboxylates,

H20 -xere prepared

pentofluoro_

However,

or o_-HCgF,)

by infrared

, no

s_pectroscopy

of triphenyltin

showing

Accordingly,

steady

it is likely

decomposition

that Ph3Sn02CR

or -HC

F f were obtained somewhat impure 64 their identification is certain from mass

spectrometry

Cmolecular ions observed),

s_pectroscopy

(see Experimental

Section).

of water in R- (Ph3Sn02C)2C6F4

and PMR,

19F NVR - , and infrared

Supporting .H20

evidence

for the

and g- fPh3Sn02C) 2C6F4. H20

has been obtained.

The PlMR spectrum of the former in deuterochloroform

showed

indicative

revealed

of

and Discussion

Prenarations

presence

[I]

compounds

of polyfluoroaryltin

We now report preparations

compounds

preparations

[ 81 , and the method has recently

10, 11-J, and no organogermanes

decarboxylation.

Results

carboxylates

syntheses

though severai

-germanium

Analogous

group

are formed on thermal decomposition

corresponding

reported,

when the organic

of other elements. are few by comparison

phenxl+liphenyllead

for the

a resonance

an endothermic

weight

of v.-ster, and thermogravimetrk loss

at 96: though loss

analysis.

of water was evidently

75 accompanied

by partial

Microanalysis

decarboxylation.

~-(Ph3SnO2C)2C6F4.H20

underwent

dehydration

suggested

on being heated

that

at 1 OO”

under vacuum. .The separations Ph@02CR-

between

(R = C6F5,

the carboxylate

E-MeOC6F4,

stretching

or R-EtOC6F4)

are comparable

for the corresponding

sodium carboxylates

@able

bidentate

bidentate

coordination.

or bridging

stretching

frequencies

triphenyllead coordinate

carboxylates

and it is probable

(see also (b)

are similar to those

Gable

of solid to those

[ 121 with

The carboxylate

1) for the analogous

carboxylate

structures

groups

have similar

with five

in the solid

structures.

have been shown to have structures

state,

Numerous

of this type [13]

Refs _ given in [ 83) .

Thermal Decomposition The products

listed in Table

isolated

Reactions

aivinq

Polyfluoroohenvltin

from the thermal decomposition

Compounds

reactions

are

2.

The triphenyltin or R-EtOC

bidentate

that the tin compounds

carboxylates

1; , consistent

[ 8j , which have associated

lead and bridging

triorganotin

carboxylate

frequencies

polyfluorocarboxylates,

Ph3SnO2CR

F ) and R-(Ph SnO C) C F .H20 64 3 2 264

(R = C6F5, R-MedC6F4,

underwent

decarboxylation

in

TA!3LEl CARROXYIATE STRETCHING

Compound Na02CC6F5

v(C02)asym

a -

1610

Ph3Sn02CC6F5 Ph3Pb02CC6F5

FREQUENCIES

1607and1583 a

Na02C-R-MeOC6F4

1581 and 1559 ’

1596

Ph3Sn02C-R-MeOC6F4

1577 and 1561

Ph3Pb02C-R-MeOC6F4a

1578 and 1559

Na02C-D-EtOC6F4=

1594

(cm-l)

dC02)

ca.

208 171

1385

211

ca.

1380

ca.

189

1383

185

1383

211

1385

Ph3Pb02C-E-EtOC6F4a

1579 and 1569

1380

[ 81 _

210

1399

1610 and 1578

From Ref.

Separation

1400 1395 and 1380

Ph3Sn02C-R-EtC?C6F4

a

sym

ca.

209 194

3RODUCTS

FROM THERMAL

DECOMPOSITION

REACTIONS

Reaction time Ou)

CarboxylatPs

Yield a>

Products

Ph3Sn02CC6F5

1

Fh3SnC6F5

65

Fh3Sn02C-g-MeOC6F4

1

Ph3Sn-pMeOC6F4

14

i + Fh3SnO2C-pMeOC6F4

5

Fh3Sn02C -pEtOC

1

6F4

4 carbaxylate

ca,

Fh,Sn

5

reactant

27

carboxylate

ca,

-t Fh4Sn

Ph3SnO2C-g-HC6F4

4 10

g-(Ph3Sn02C)2C6F4.H20

trace

reactant

reactant

carboxylate

ca.

carbcxyiate

10 a

81

E- @h3Sn) 2C6F, f

50

47

Ph$n-E-EtOC6F4

t

15 a

Fh3Sn-pEtOC6F4 f

Fh3Sn02C-z-EtOC6F4

?h Sn 4 reactant

Fh3Sn-EHC6F4

15

4

Fh3SnF

&PhHgO2C)2C6F,-

2

g-PhHgC6F4C02HgPh

85

c- (PhHgO2C)

2

E-@h

68

c- (Ph3Sn02r,)

2C6F,

2C6F4

[Ag02CC6F5

C F 2 64 E- (Ph3PbI 2C6F4

5

E-(Ph3Fb02C)2C6F4

c Ph3GeBr]

s. Hg)

f

Ph3Fb-g-HC

t

Ph4Pb

3

Fh3GeC6F5

15 6 F,

12 68b 25

[Ag02C-pEtOC6F4

f Fh3GeBr]

6

Fh Ge-g-EtOC F , 3 (Ph3Ge) 20, PhzGt

c

[ ~&TO~C)~C~F~

t 2 Fii3GeBr]

7

x?fPh3Ge12C6Fq,

c

Fh3Ge-pHC6F4,

Bh3Ge120,

Ph4Ge

E Major orsanometallic b

8ased

product;

on p$h3Pb02C)2C6F4

c Mixtures

of products

obtained;

yield not determined. 3

Ph4Pb yields

i

Ph2FbC&(02Cf2C6F4j

not determined.

.

77

- . bofl&~&i~ine i

&fcrding

compc+nds; _-:j _

the corresponding

Ph$nO2CR

- : _ _

g- (Fh3Sn02C) 2C6F, Identification of the *ajor for suitable

1161-

CO,

readily

f

e.g.

2C0

Section).

followed

[ IS] .

(3)

2 data,

bi)

and

Assignment

straightforwardly

diphenylthallium

(III) halides

(2)

from analytical

(Experimental

spectra

compounds,

bis (pentafluorophenyl)thallium showed

followed

in the infrared

reference

f

z-@h3Sn)2C6F4

I 2

19 F NMR spectra

and

peaks

Ph,SmR

-

of the compounds

in.i%ared, mass,

polyfluorophenyltriphenyltin

from data

halides

[ Id]

The mass spectra

and

generally

behaviour

similar to that reported for pentafluorophenyltriphenyltin 19 F NMR spectra were based on published chemical Assignments of the

shift data r17l _ Thermal decomposition

of Ph3Sn02CR

Or = R-MeOC6F4

tetraphenyltin

in addition

derivatives

The formation of tetraphenyltin

.

disproportionation

2 Ph3Sn02CR

Neither

diphenyltin

derivatives

benzoate

-++

be hydrolysis

or hydrolyse

Ph2Sn (02CR) 2

(4)

Ph4Sn _

+

Ph2SnR2

(5)

nor bis (polyfluorophenyl)diphenyltin

of E- (Ph3Sn) 2C6F4,

was obtained

X20

-d

of bis (triphenyllead) acetate

Both p-(Ph,Pb)2C6F,

tetrafluorobenzene

i

resulted

acid,

in the tin system. whereas

Thermal decomposition in decarboxylatfon

Ph3SnOH

; prepared

were obtained,

(major product) was isolated,

tetrafluoroterephthalate

chromatography_

tetrafluoroterephthalate

and Ph3Pb-R-HC6F4

of

The origin of this compound may

with tetrafluoroterephthalic

did not give tetraphenyltin.

a low -yield of triphenyl-

Ph3Sn-R-HC6F4

latter being greater than the proportion tetraphenyllead

of diphenyltin

from thermal decomposition

of the major product during thin layer

of triphenyllead

decompose

[ 183 ) .

tetrafluoroterephthalate.

+

probably

on work up (ready hydrolysis

to the high yield

rr-(Ph3Sn)2C6F4 Pyrolysis

+

but the former co.mpounds would

2,3,5,6-tetrafluorophenyltin bis (triphenyltin)

to the

Ph4Sn

dicarboxylates

has been observed

In addition

can be attributed

(4) or (5).

e

were isolated,

further in pyridine

gave

to the p-alkoxytetrafluorophenyltriphenyltin

reactions

2Ph3SnR

or R-EtOC6F4)

(6)

by reaction

was also examined. the proportion

of the

In addition,

R-(Fh3Sn02C)2C6F4

of di(phenylmercuric) giving E-df (phenylmercuri)-

fn high yield.

$M’hHg02C)2C6F4

-

2 CO2 + g- (Ph.Xd2C6F4

(7)

78 Attempted recrystallization

of this compound gave a less

pure product possibly

owing to disproporticnation. ~-(PhHg)2CSF,

Ph2Hg

-

+- fll-HgC9P4j;

A a-tetrafluorophenylenemercury decarboxylation

high melting

spectroscopy

[ 193 .

(9) followed

of bis (triphenyltin)

solid,

identified

A possible

by elimination

substituent

polymer has previously

of mercuric tetrafluoroterephthalate

The,rmal decomposition insoluble

03)

tetrafluorophthalate

as triphenyltin

reaction

fluoride

path comprises

of *h-hefluorine

been prepared

by

[ 51 _ gave. an

by infrared

hemidecarboxyiation

ortho to the bulky triphenyltin

(10).

F

0I F

CO2SnPh3 (9) C02SnPh3

CO

-

F

+ 2-F

F

/

C02SnPh3

\

SnPh3

(1;) A

F

F F Ph3SnP

t F

Suppoti for this path comes from the obser=tion tetrafluorophtnalate

gave phenylmercuric

that di(phenylmercuric)

g- (phenylmercuri) tetraftuorobenzoate

on thermal decomposition_

/I 0 F

F P

\

F

CO2HgPh C02EgPh

kc0

2

C02HgPh

F\

HgPh

The product was equal intensity

indicative

multiplets

acids

Thus,

.

19 F XMR spectrum,

The lowest

are characterized

which

field resonance

by preferential occurs

and sodium phthalates,

one molecule

decompose

by the

hemidecarboxyiation

mercuric acetate loses

identified

was

showed

four

in a position

for a fluorine ortho to a heavy metal [ 20) , and showed satellites 199 of Hg-P coupling. Decarboxylation reactions.of mercuric salts

of phthalic E2!.

(11)

F

F

appropriate

01

F/ +

loss

in the Pesci

of one carbon dioxide reaction

and mercuric tetrafluorophthalate

of CO2 at 220° giving+_-HgCSF4C02j3,

into+_HgC6F4+3

[ 211 between

until 300° [ 223 .

which does not

79

(c)

Thermal~Decom&osition

Reactions

giving

PoWluorouhenYlsermanium

Compounds Reaction refluxing

of silver

pyridine

presumably

_pentafluorobenzoate

with bromotriphenylgermane

gave pentafluorophenyltriphenylgermane

by formation and decarboxylation

@able

in

2))

of triphenylgermanium

pentafluorobenzoate. Ph3GeBr

t. Ag02CC6F5

By contrast,

reaction

nuorobenzoate Gable case,

and disilver

to Ph3Ge-p-EtOC6F4

oxide after t-1. c. of the reaction

NMR spectroscopy

germanes

probably

.

formed by partial

+

The formation of tetraphenylgermane germane

(Table 2) can be explained

corresponding

(d)

gave other products

organotin

preparative

compounds

Utility

-germanium

mixed with bis (triphenyl-

product,

identified

hydrolysis

decarboxylation

of

+

@able

[reactions

manner to formation of the (4) and (611.

for PolYfluoroDhenYl-tin

Ph3Sn-g-MeOC6F4

attractive

alternative

simplicity

with the previously

were obtained

and

for carbon dioxide

elimination

on the use of decarboxylation

The substituent

effects

and

An

conceived.

prior synthesis

of

by preparative

of PhgSn02C-c-HC6F4 that two fluorines

Griqnard

yield.

is not readily

method would require

it appears

reported

are new compounds,

6F4X (X = Br or I) , which have to be purified Since decarbo>rslation

by

of the procedure

in satisfactory

route to Ph3Sn-R-MeOC6F4

or organolithium

could not be effected,

bonds.

obtained

The other polyfluorophenyltins

all except

restrictions

9

and triphenyl-2,3,5,6-tetrafluorophenylin a similar

2) and the comparative

[ 24, 251 .

are essential

Ph3GeOH

Compounds

should make the method competitive

The Grignard

by

spectrum

of the polyfluorophenyl-

E-HC6F40Et

Decarbox~lation

synthesis

C261 -

and was identified by the infrared

The high yield of pentafluorophenyltriphenyltin

Q-MeOC

In each

-HZ0

H20

+ CO2

E-ethoxytetra-

during chromatography.

i Ph3Ge-E-EtOC,F4 0 -

e.g.

Ph3GeC6F5

and E- (Ph3Ge12C6F4.

was obtained

The germoxane,

+

with silver

tetrafluoroterephthalate

the polyfluorophenylgermane

[231 I was

[ Ph3Ge02CCgF5]

of bromotriphenylgermane

2) in addition

germanium) “F

f

+ AgBr

g

.l. c.

and g- (Ph3Sn02C)2C6F4 ortho to the carboxyl.group

to occur,

thus imposing

in formation of polyfluoroaryl-tin

are consistent

with electrophilic

attack of

80

tin on an organic the transitfon

group whichrdevelops

Similar restrictions

.

+-Ph

Ph3 Sn ‘*” --“\;+z~ =. -. ._ $y_- .--

probably

polyfiuoroa~lgermanes

also apply

In addition,

can be obtained

method [ 24

character

gives

conveniently

a higher yield.

use of any elimination

in

carbon bonds.

Unsuccessful

decarboxylation

have been re&-ted

2

preparations

of

the present

to.

Although

compounds.

by decarboxylation,

reaction

CO

are more susceptible

organotin

However,

first successful

SnR + 3

to decarboxylation the products

on work up than the corresponding

Ph3GeC6F5

carbanionic

state.

3

hydrolysis

considerable

the Grignard

preparations

are the

in the formation of germanium-

attern_pts to obtain perfluoroalkylgermanes

by

[ 28, 291 _

Experimental M icroanalyses Entiared spectra

were by the Australian

(4000-400 cm-‘)

diene mulls were recorded

of compounds

on re_ported data

-Nere obtained shifts

with a Bruker WlI-90

Mass

from CFC13 ?‘P). beam, intense given.

double focussing

were obtained

instrument _

Each listed

terephthalic

Utiecht,

Tetraphenyllead

stored over molecular

More request

m/e value

sieves.

Triphenyltin

details

to the authors.

at least

15% of the * are given,

of intensity. acid,

and tetrafluoro-

and bromotriphenylgermane Chemisch

iiom Fluka.

hydroxide

[ 311 , 2,3,4,

oxide

of the infrared and mass spectra

was

Institut,

Pyridine was

under nitrogen

hydroxide

acid [ 323 , bis (triphenylgermaniumf

complete

is the most

100% abundance)

was obtained

from potassium

Chemical

-pattern for the assignment

was from the Organisch

and tetraphenyltin

over and distilled

tluorobenzoic

tetrafiuorophthalic

acid were from Bristol Organics,

from ROC -F!IC _

refluxed

(assigned

are given irrespective

acid,

were

NMR spectra

with anAE1 MS 30 double

with the correct isotope

that molecular-ions

Only

i II) or upfield

Only -peaks above m/e 197 @hSn+) with intensities

Pentafluorobenzoic

T.N.O.,

[ 14, 153 ).

from tetramethylsilane

main peak of the most prominent cluster except

and hexachlorobuta-

or a Varian A56/6QA instrument_

downfield spectra

peak of a cluster

Melbourne.

180 spectrophotometer. * are listed. Assfgmnents (below)

[ 301 , other vibrations

(v(C02)

are given in p.p.m.

as Nujol

Service,

with a Perkin-Elmer

bands of medium or greater intensity based

M icroanalytical

and was S-tetra-

[ 333 , silver

are available

on

81 pentanuorobenztite

[ 341 , and the 4-alkoxy-2,3,5,

[ 8,. 351 were~ prepared tetraf&orobenzoate

by reported

and disilver

mettod used previously

methods.

Silver

for silver

(ncj _

1.9.

CQH,$gF403

calcd.:

C,

299&n,

1703m (shj,

1653~s.

ca.

and 1482Vs,

1419 and 1390~s [vs(COzj]

H,

and QQOvs, 945s, Disilver

817s,

C8Ag2F404

calcd.:

r vas (CO,)1

, ca.

C, 21.3%).

boiled

(ca.

purification.

carboxylate

(ca.

complexes

gm) in pyridine

plates @:I mixture ofEeselge1 times and yields givenwith

are listed

(ix) 766m,

rjolyfluorocarboxvlates

and the appropriate

in vacua.

was effected

and were used

HF254 and Kieselgel

G : Merck).

purification

compounds

All

was

by heating the.

in benzene

the individualcompo=nds.

acid

quantitatively

(5 ml) under nitrogen.

2, detailed

IO28

21.1.

, 985~s 0x),

was dissolved

in Table

(brj,

1565~s

were obtained

of the solvent

removed in vacua and the residue

was

hydroxide

Thermal decomposition

1.0’2.0

ca.

C,

1505

75 ml) were mixed and the solution

The carboxylate

as white -powders upon evaporation without

(Found:

of triohenyltin

amounts of triphenyltin

for 30 miri.

~300~

(br) [vs(C02j]

and thermal decomoosition

in hot methanol

Infrared

Cv,,(C02)l,

II37

1390~s

ca.

1 .S%j.

0

absorption:

(a)

each dissolved

H,

Infrared

741 and 722vs,

Stoichiometiic

31.3;

M.p.

(br), -1 494s cm .

Preparation

by the

M . p- 2 OS0 (dec _) (Pound:

and 1120~s -1 723m, 506m (br) cm .

(xx).

1475~s

6-

were prepared

1560~s

, 1277s.

767 and 755vs,

tetrafluoroterephthalate

acids

pentafluorobenzoate.

absorption

32.0;

4-ethoxy-2,3,S,

tetrafluoroterephth.&ate

Silver 4-ethoxv-2,3,5,&tetrafluorobenzoate C,

Gtetrafluorobenzofc

The solvent and put on t.1.c. Reaction

procedures

being

were obtained as white

crystals. Trinhenyltin nentafluorobenzoate H,

2.9.

C25Hl 5F502Sn calcd.:

calcd . : C,

51.9;

H,

1607 and 1583vs

1481s,

1471s,

1123s,

1109s,

1432~s

Ph2SnC

[v(CC)]

F “);

PMR

spectrum

(m, ZF, F 2,6), :

150.9

(Pound:

C , 52.9:

C25H1 5F502Sn..H20 3070 and 3055m [u(CH)i

1566~s;

1533s, 0

1522vs,

Cv,(CO,)]

1495vs

934m, 829m, 765 and 76Os,

485 (100, Ph2Sn02CC6F5+),

287 (19, C,F,Sn+),

(GDC13j:

with D20_

fm, 1F. F 4),

ca. “F

161.8

75Os,

yJ cm -1 .

441 (31,

274 (19, Ph2Sn+),

7-6 (m, Ph) p-p-m., NMR spectrum Gn, 2F. F 3,5j

, (brj,

, 1304m,

663m, SOQm, 450 and 440s [X-sens.

293 (61, Ph,SnP+j,

(46, PhEn’).

H, 2.7.

absorption:

(brj [v(CFjl,

m/e 562 (2%, M+j,

after shaking the solution

126-128O

, I395 and 1380~s

, 695~s [@(CC)],

spectrum:

53.5;

(brj [v~,(CO,~I,

1078m, 995~s

727~s [v(CH)]

C,

M _p.

Infrared

3.0%).

1655s,

Mass

(ncj .

197

unchanged

(CDC13):

138.3

p.p.m.

Thermal

52

decomposition:. Elution cif the benzene (9:l V/V) gave one mobile band, Recrystallization 85O, lit. C,

[24]

55.7:

&om ethanol m.p.

Triphenyltin (Found:

C,

with acetone..

gave pentafluoroohenvltiphenvltin, C,

The infrared

were in good agreement

spectra

with light petrol/acetone

which was extracted

86O (Found:

H, 2_9%).

solubles

55.8;.H,

P

(ncj .

52.9;

C,

C26H18F403Sn.H20

3.6.

3070 and 305&n [v(CH)] 1507s and 1485vs, 1283 and 126&i,

C26Hl SF403Sn calcd.:

calcd.:

C,

52.3;

, 165Os,

H,

, ca.

calcd.:

NMR

[29]

M . p. 102O

54.5;

Infrared

3.4%).

1597s (shj,

1432s [v(CCj]

84-

data.

4-methoxv-2,3,5,6-tetraftuorobenzoate H,

m-p-

CZ4y45F5Sn

3.0.

C241 . mass [ 153 , and

xvi&&reported

,

H,

3.2.

absorption:

1577 and 1561~s [v

1380~s

1195m, 3129 and 1120s [ v(CF)I

Ibr) Ev,(CO,)l

(CO,)]

I

, 13”3”7~(SW,

, 1078m, 1024m, 998vs and

977s [ v(CF)]

, 75Os, 730~s [ y(CHj] , 695vs [@(CC)1 , 684m, 449s -1 yJ cm _ Mass spectrum: m/e 574 (2%. M+), 497 (100,

[X-sens.

Ph,SnO,CC,F,OMei) (35, PhSn+j .

, 453 (52, Ph,SnC,F,OMe+j

PMR spectrum unchanged

15H, Phj p.p.m., spectrum

(CDCl,):

139.7

Thermal decomposition:

m-p.

sample).

Recrystallization

3 .,4-

C,

224-22S"

57.3;

F , la-. 4%j .

1634s,

[ 4 (CC)]

Infrared

spectrum inkared

4.07

extracted

(s,

(CDC13j:

solubles

m. p. 222-224O.

hand from ethanol

(nc) , m. p. 89O calcd.:

C,

3070 and 3050m [ v(CHj]

(brj,xi430vs

[v(ZCj]

, 1368s,

56.8:

H,

, 2945m, 1193m, 1100

97Ovs [v(CFj] , 936m, 731~s [Y(CH)] , -1 m/e 453 (lOO%, $J cm _ Mass spectrum:

, 1025m, 997s,

A molecular-ion 3H, 0CH3), 120.3

cuboxylate

_

(ii)

with light petrol/acetone with acetone _

293 (44, Ph,SnF~), cluster

ca.

7.5

274 (21, Ph,Sn’,

was not observed.

156.1

S hr reaction_ (9:l

NMR

p.p.m.

The

similar to-that of

Elution of the benzene

v/v) gave two bands,

The faster-moving

“F

(m, 2F. F 3,5)

from the bottom band was

,

PMR spectrum:

(m, 15H, Ph) p.p.m.

(r-n, 2F, F 2,6),

spectrum of the material

the reactant solubles

1460~s

351 (26, Ph,Sn+),

197 (49, PhSn+) . (CDC13j:

G25H18F40Sn

absorption:

p.P.m.

identical with that of an authentic

.

F, 13.6.

(m,

lgF NMR

which were extracted

of the product Tom the second

, 448 vs [X-sens.

Ph2SnC6F40Met).

(m, 2F, F 3,s)

, 197

7.7

with D20.

hand was tetraphenyltin,

(infrered spectmm

3.7;

ca.

Elution of the benzene

6-tetrafluorooh&vltrinhenvltin

1495vs and 1484s,

and 1078~s [v(CP)] 70&s

H,

3H. OCH3j,

(85: 15 v/v) gave three bands,

Lit. [36aJ

(Found:

158.5

1 hr reaction.

The fastest-moving

gave 4-methoxv-2,3‘S,

(s,

after shaking the solution

(m, 2F, F 2.6). (i)

with light _petrol/acetone with acetone.

4.12

(CDC13j:

, 293 (42, Ph,SnF+j

which were

band was tetraphenyltin

(infrared

. 83 identification), hand was

while the infrared

spectrum of the product from the second

similar to that of the reactant

carboxylate.

Trinhenyltin

4-ethoxy-2,3,5,6-tetrafluorobenzoate

(Found:

54.0;

C,

H,

3.8.

M . p. 103-l OS0

(ncl.

C27J120Fq03Sn

calcd.:

C,

55.2;

H,

3.4.

Infrared absorption: F 0 Sn.H20 calcd.: C, 53;6: H, 3.7%). C27?O 4 3 3063 and 3045m [ v(CH)l , 2992m, 1648vs, 161 Ovs 0x) and 1578~s [v,,(CO$,

1562vs,

[vi(CO,)]

, 1333s

and 992vs

Ox-) L v(CF)l

(sh),

1481vs,

1283m, 1260m, .1125~s

511 (100, Ph2Sn02CC,F40Etf),

Pb3Snt),

293 (83, Ph,SnF*)

15H, Ph) p.p.m_, spectrum

4.37

140.0

(CDC13):

(m, 2F, F2,6), (i)

with light petrol/acetone

identification).

Recrystallization

351 (27, (CDC13):

157.9

ca.

(m, 2F, F 3,5)

3.7;

C,

57-4;

H,

Infrared

F, 14.0%).

1633m, 1491 and 1481s, 1362vs,

3.8;

absorption:

1460~s

(lx),

726~s [y(CH)] spectrum:

PhSnC6F40f),

“F

(m, 15H, Ph). (m, 2F, F 3,5)

4.31

NMR spectrum

p.p.m.

The infrared

which

solubles

were extracted

s_pectrum ofthe

carboxylate.

carboxylate.

with acetone.

57.5;

, 2990m,

[ v(CF)] , -1 cm . Mass

A

361 (16,

PMR spectrum

(m, 2F, F 2,6),

(CDC13): ca.

7.5

155.4

1 hr reaction.

(ii) petrol

0 : 9 v/v)

Recrystallization

gave two

from ethanol

band gave 4-ethoxy-2,3,5,6-w-

m. p. 63o (infrared identification)

productfromthe

C,

2H. 0CI12CH3),

120.5

with acetone/light

of the product from the faster-moving fluorophenyltriphanyltin,

calcd.:

spectrum of the product from the third

similar to that of the reactant

Elution of the benzene

(9, L~Hz,

(CDC13):

solubles

997s, 957vs

197 (50, PhSn+).

3H, CCH2Cg3),

NMR

bc) , m. p.

467 (100, Ph2SnC6F40Et*),

293 (43, Ph,SnF*),

(t, L7Hz,

band was

M+),

“F

, 139Os, 1369s and

, 446 and 438s [X-sens.

, 695vs [$(CC)]

m/e 544 (c l%,

[v(CC)I

, 1061m (sh),

1091~s and ‘-075s [ v(CF)l

(m,

(ineared

3065 and 3050m [v(CH)I

1428~s

7.7

of the product from the

C26H20F40Sn

F, 13.5.

1.40

which were extracted

band was tetraphenyltin from ethanol

_

p.p.m.

Elution- of the benzene

hand gave 4-ethoxy-2,3,5,6-tetrafluorophenvltriphenvltin

63O (Found:

reactant

, 1079m, 1020s

with D20.

(85: 15 v/v) gave three bands,

The fastest-moving

bands,

(lx)

2H, 0CH2CH3),

the solution

5 hr reaction.

with acetone.

1.41

(br) [ v(CF)]

PMR spe&um

.

(q, L 7 Hz,

after shaking

unchanged

The-ma1 decomposition:

second

, 1385~s

467 (56‘, Ph2SnC6F,0Ett),

, 197 (86, PhSni)

3H, 0CH2CH.&,

(t, L 7 Hz,

H,

1430~s [ v(CC)]

, 767 and 760m., 747s, 730~s CY (CH)I , 695vs -1 , 445 and 440s [X+sens. yJ cm . Mass spectrum: m/e 588 (3%.

[+(CC)] M+),

1504s,

second

bandwas

_

The infrared

similartothat

ofthe

84

eiphenyltin

C2SH16F,02SnqaIcd.:

54-O; H, 2.9.

C25H16F,02Sn.H20

and1561vs,

1525vs,

M-p.

(sh), 1635 and 1625~s;

Infraredabsorption: (sh), 1578 [vas (CO,)]

1606~s

[v(CC)] I 1400 andf378vs

1431~s

1480~s.

1306 and1296s,

IOO-1020 (Found: C,

C, 55.3; H, 3.0.

C, 53.5; H, 3.2%).

c&cd::

3072x11[v(CH)], 1650~s

[v,(CO2)]~

(ncL

2,3,4,5-te*JaSuorobenzoate

&x1

1265vs, 1190m. 1099vs, fO76vs, 1036~s (br)

Cv(CP)] , 9g7s, 929vs [v(CF)], 895s, 805m, 79Ovs, 778vs, 765s, 734~s p(CH)], 728s, 697vs [+(CC)], 674m (shJ. 66lm, and 441~s [X-sens. d,

430s cm

-1

Mass

.

PMR

spectrum

(CDC13):

293 (39, Ph2SnF+),

ca. 7.7 @-I,Ph and -CgF4) "F

unchanged aftershakingthe solutionwith D20-

p.p.m.,

452

s_pectrum: m/e 544 (3%, M?,

467 (100, Ph SnO CG HF, +), 423 (16, Ph2SnC6HF,ff. 2 2 6197 (28, PhSn*).

br),

554s and 543m

KMR

spectrum

137.4 (m, lF, F2 orF.5). 139.4 (m, IF, F2 orF5). 252.3 (m,

C (CD,),SO]: lF, F3 orF4).

155.2

Thermal decomposition:

(m, lF, F3 orF4) p.p.m.

Elution of the benzene soluble product with acetone/light petrol (2:3v/v)

gave a broad poorlyresolved bandwhichwas infrared spactrum ofthis product was

extractedwith acetone.

The

si.m*Xarto that of the reactant

carboxylate. Sis(triphenyltin) 2,3,5,6-tetrafluoroterenhthalate hydrate (nC1. 32O (Pound: C, 55.2; F, 3.8. C44H30P404Sn2

H, 3.4,

[v(CE)]

3070n

, 1624~s

C,,H30F,04Sn2.H20 __

calcd.:

C, 56.5;

(sh), 1600~s

15OOm,

14SOs,

1450s;

125Sm,

1081s,

1025m, 998s and 99Ovs [v&X')1

I(p(CG)l , 480m, C6F4C02SnPh2

450~s

1432~s

[X-sens.

cm

-1

1377~s

.

Infrared absorption:

, 1582~s

(sh), 157Ovs,

0x1 [vs(c02)],

1336m

, 730~s CY(CH)],

Mask

spectrum:

309 (31, C12H10FOSn+~,

m/e

NMR

at

696vs 466 (18%,

293 (100,

The

3.45 p.p.m. disappeared upon shakingthe solutionwith D20.

spectrum (CDC13): 139.1 (s, C.&I

p.p.m.

The residue after evaporation ofthe pyridine was

putont.1.c.

(sh),

Amolecular-ion clusterwas not observed.

spectrum (CDC13): 3.45 (s, H2OI, ca. 7.7 (m, Ph) p.p.m,

resonance

"F

d

+), 351 (88, Ph3Snf),

Ph2Snl?+I,197 (60, PhSn?. PMR

[v(CC)],

230-

calcd.: C, 55.4:

H, 3.2%).

(br)[v,,(CO,)]

M-p.

plates.

Elutionwith lightpetrol/acetone

bands, which were extractedwith acetone.

Thermaldecomoosition:

dissolved in chloroform and

(4:1v/v) gave two

The faster-moving bandwas

tinhenvl-2,3,5.6-tetrafhroroohenvltinnc , m-p. 90-93O (J?oun& C, 58.5; H, 3.6. 500

(e

C24H16F4Sncalcd.:

C. 57.8; H, 3.2%).

Mass

spectrum:

m/e

1%. M+), 423 000, C HF,SnPhZf), 346 (IS, C HP,SnPh+), 293 (48,

Ph,SnF*), 197 (29, PhSn+).

61giNMR _

P 2,6j, 137.8 (m, 2F, P 3,s) p.p.m.

snectrum _ (CDC! ): 120.0 (rn,2F, 3 Recrystallizationfrom benzene-ethanol

85 of the product from the second phenyistannvl)benzene c42H30F4sn2 3062m [ v(CH)] 1025m,

(ncz, m.p.

calcd .:

999s,

436s [X-sens.

C,

, 148Os,

59.5;

351 (100, Ph3Sn+),

Bis (triphenyltin)

, 1418vs,

NMR spectrum

L 21.4 Hz,

-C6F4-)

59.7:

H,

3.6;

Infrared 1381s,

F, 8.6.

absorption:

1206vs,

1075s,

(Pound:

3056m [v(CH)],

C,

(ca.

57.7;

168Ovs,

(CDC13):

(nc).

after evaporation

A molecular-ion 118.6

(s, with

p.p.m.

3,4,5,6-tetrafluoronhthalate

After drying

158-160°

C,

P, 9.0%).

197 (69, Ph Sri+).

“F

as a monohydrate

3.3%).

3.6;

1432~s [v(CC)]

cluster was not observed, 117SnF,119 SnF satellites

H,

236O (Found: II,

(tri-

927~s [v(CF)l, 730~s [y(CH)], 696vs [#(CC)], 559s, 449 and -1 m/e 771 (21%. yJ , 406 m cm a Mass spectrum:

Ph,C,F,Sn,+),

isolated

band gave 1,2,4,5-tetrafluoro-3,6-bis

The carboxylate

of the methanol

pound:

1 OO”, C 10e2 mm Hg) , the complex H,

1651~s

3.0%).

Infrared

absorption

1127m,

1075~s

[v(CF)],

78Ovs,

763vs,

732~s [y(CH)], 699vs [+(CC)l, 665m, 652m, 560m and 543s, . -1 d , 420m, 333m, 294m (sh), 27Ovs, 238s, 220s cm . Mass

spectrum:

A molecular-ion

(CDC13):

137.7

decomposition:

cluster

(m, 2F, F 3,6),

Preparation

by reaction lead acetate

was effected

2,3,5,

(dec _)

C,

2_7%)_

Infrared

absorption:

1493m, 1474vs,

47-4:

H,

by heating

1435~s [u(CC)]

2.8.

as

tetra-

were prepared

acetate

or triphenyl-

Thermal decomposition

in dry pyridine

in Table

2, isolation

under nitrogen. and purification

compounds. (nc).

C441130F404Pb2

3055m [ v(CH)] , 1380~s

Thermal

bis (phenylmercuric)

&tetrafluorotereph+Slalate

(Pound:

NMR spectrum

tetrafluoroterephthalate

being given with the individual

Bis (trinhenvllead)

197 (30,

of mercuric and lead carboxvlates

acid in hot methanol.

are listed

810m,

[ 191.

amounts of phenylmercuric

with the appropriate

832m,

filtered offandidentified

tetrafluoroterephthalate,

Reaction times and yields

“F

1195m,

On, 2F, F 4,s) p.p.m.

infrared spectrum

of stoichiometric

930m,

C,,H,,FOSn~),

not observed.

151.9

, and bis (triphenyllead)

of the carboxylates

procedures

was

and thermal decomposition

Bis (phenylmercuric) fluorophthalate

309-08,

The insoluble product was

triphenyltin fluoride bythe (b)

998s, 951vs Cv(CF)I;

m/e 351 (lOO%, Ph,Sn+),

PhSn+) .

126Ovs,

1475vs,

[v(CC)],

1026m,

1299vs,

152Os,

cm-‘):

1432~s

447~s [X-sens.

[v,(CO,)],

55.2;

had m. p.

(4000-200

(br)and 1633s [vas(C02)],

1390andl350vs

was C,

, ca.

M. p. 282-283O

calcd.:

C,

1600 [ vas(C02)]

cbr) [v,(CO,)]

, I255m,

47.5;

H,

and I57Ovs, I065m.,

997 and 985vs fv(CF)] , 735 and 726~s [y(CH)] , 692vs [@(CC)], 474-s, -1 Thermal decomposition: After removal of the 440~s [X-sens. yJ cm . 1019s,

pyridine giving

in vacua,

ihe product was recrystallized

tetra_nhenyIlead,

identical

m-p.

lit.

223-22Sb,

with that of an authentic

from a toluene-p&r01

[ 36 fb)]

sample).

The filtrate

'&e recovered product was

dissoived inchloroform

E!_ution with acetone/light

petrol

band was tetraphenyllead

0:4 v/v)

_

kj,

3062s [v(CH)]

[v(CC)],

lL86s,

147Ovs,

1165.5, 1062m,

1017s,

1430~s

m/e

spectti:

588 (<1X,

Mf),

661m,

(m, ZF, F 2,6), 137.8

[X-sens.

C42H30F4Pb2 [*J(CH)],

calcd.:

3042m

(sh), 1573m,

1430~s

1477s,

1300m,

1185vs,

1063m,

1019s,

[ Y(GH)]

, 693~s

[@(CC)]

, 548s,

438~s

m/e

1024

(cl%,

(47, Ph3Pb+), spectrum

M+),

1213s,

J/J cm-l.

'SF NMR

spectrum

Pound:

C,

3070s.

[v(CC)]

137&s,

995vs,

and 141Os,

920vs [v(CF)J,

[X-sens.

(s, -C6~A-)

H,

Infraredabsorption:

947 (29, C6F4Pb2Ph5+),

117.7

(CDC13):

49.2;

yJ cm-l.

Mass

spectrum:

510 (23, C6F4PbPh2+),

The products

p.p.m.

2.9.

725~s

28: (78, PhPbf,, 227 (26, PbF+), 208 (100, Pb+L

(CDC13):

Mass

Recrystallization from

236O-238O

H, 2.9%).

133Om,

1328m,

band gave l-,2,4,5-tetraauoro-3,6-

(r-x), m.p.

C, 49.2;

absorption:

+), 357 (45, C6HF4Pb+j,

(m, 2F, F 3,s) p.p.m.

bis(trinhenylnlumbyl)benzene

band gave

896~s [w(C-F)]. 854s, 723~s

440~s

511 (74, Ph2PbC6HF4

product from the fourth

light petrol ofthe

plates,

Infrared

1348vs,

285 (36, PhPb+), 22; (43, PbF+), 208 (100, Pb+). lLS.2

and

The fastest-moving

The second

m. p. 97O.

999vs [v!cF)],

['((CH)], 705s and 694vs [@(CC)],

spectru&

was evaporated

gave six bands.

triDhenyl-2,3,5,6-tetrafIuoroDhenvlle&d

(infrared

and put ont_l,c_

(akfrared identification)

, 157Sm,

227-228’

mixture

439

"FNMR

from the remaining

bands were not obtained in sufficient yield for identification, Eis (ahenylmercuric) 2,3,5,6-tetrafluoroterephthalate (Found: C, 30.4; H,

1.3;

1610~s 1217s

H,

1.5; F, 9.6.

1475vs,

1431s [v(CC)],

(sh), 1272m,

1242vs,

1214m,

1080m,

, 695~s [@(CC)],

precipitate

was filtered

C,

30.1;

H,

Infrared

absorption:

[v(GC)]

, 137lm,

(sh),

1624 and

0x1 [v,(CO,)],

1358~s

(ca.

200 ml) and the

and dried in vacua (nc), m.p.

, giving

> 300’

C

H -F Hg2 calcd.: C, 30.7; H, 1.4%). 18 10 4 3065 and 3050m [v(CH)] , 1625m, 1426 and 1410~s 1.8.

>2OOvs,

H,

C, 30.4;

1025s, SSOvs [v(CF)], 753 and -1 Thermal decomDosition: .

with petrol,

1023m, SSSm, 916vs [ v(CF)] 560m,

442m,

409m

ofthis product from atoluene-nitrobenzene 28.1;

> 300°

445~s cm

(phenylmercurijbenzene

694vs CQ(CC)],

C,

1657~s

poured into light petrol

off t washed

1,2,4,5-tetrafluoro-3,6-bis (Found:

521vs,

M-p.

calcd.:

(sh),

1575s,

The cooled reaction mixture was

(Found:

1660s

[v,,(CO,)],

734~s [Y(CH)]

[y(CII)],

C20H10F4Hg204

Infrared absorption:

F, 9.6%).

(nc).

1.5%).

cm-l-

, 740m and 727~s

Attempted recrystallization

mixture gave a&pure

product

Bi& (ohenylmercuric) slow

-3,4,5,6-tetrafluoroohthalate (Found:

decomposition.

1644vs,

1610~s

C,

(br) [v,s(CO,)],

[ v(CC)]

, 1402~s .(br) [ vs (CO,)] , 1026s,

decomposition:

reaction

was evaporated

fluoro-6-ohenylmercuribenzoate 3065 and 3055m [ v(CH)] and 1479vs,

1455s,

[w,(CO,)],

M . p . > 2 3 o”, with Infrared

1481vs,

, 1356 and 1.332~~~ 1267s,

952~s [v(CF)]

The cooled

and the filtrate

,924s,

absorption:

1436 and 1433s 112Os,

1075~s

841s,

770 and 761vs, 726vs, -1 419s cm . Thermal

mixture was poured into light petrol

qiving

insoluble

phenvlmercuric

(nc) , m. p. > 3 OO”.

2,3,4,

Infrared

S-s-

absorption:

, 1620s (sh), 161 Ovs, 1558~s (br) Cv,,(CO,)]

1446s and 1431~s [v(CC)]

, 1370 and 1355~s

, 1486

0x1

1030s

, SSSm, 906m, 798m, 777m, 767m, _:54~,~9735 and 730~s [Y(GH)I , 645m, 451m [X-sens.

C (CD3) 2m]

115.0

:

(m, lF,

F 2),

(m, with

yJ cm

?.50.2 (m, lF,

,

F _NMR spectrum

.

199 HgF satellites

(ca.

product was filtered

1310m, 1270m, 1220m, 1090m. 1071m, 1049m. ca.

693s [+(CC)]

131.3

1516s,

A small quantity of an unidentified

200 ml).

[ v(CF)]

1.4%);

620m, 551m, 53Os, 455 and 448s,

715m, 694vs,

off,

H,

1578vs,

[v(CF)]

lOOOs,

30.0;

(kc) .

Lea.

250 Hz,

F3 or F4) and 155.4

(m, lF,

lF,

F 5).

F3 or F4)

p-p-m. k)

Decarboxylation

syntheses

Eromotriphenylgermane silver

salt were refluxed

-cooled

solution

to the filtrate

which was filtered Detailed

plates.

and the stoichiometric in dry pyridine

was filtered

usually

of oroanogermanium

from silver

resulted

off.

lization [27] 61-2:

bromide.

The filtrate was

band,

H,

114-116O

of additional

concentrated

which was extracted

C,

The

of dichloromethane silver

bromide,

and then put on t -1. c. compounds.

with acetone.

compound,

(9~1

Recrystal-

m. p. 116-l 17O, lit.

H, 3-S. C24H1 5F5Ge calcd.: C, 19 F NMR [ 201 spectra were in The knfrared [ 271 and

3.2%).

(Pound:

Addition

3 hr .

Elution with light petrol/acetone

from light petrol gave the required

m-p.

for ca.

is given with the individual

Pentafiuorophenyltriphenylgermane. v/v) gave one mobile

amount of the appropriate

under nitrogen

in precipitation

product analysis

comoounds

62.1;

good agreement with reported data, except the absorption noted [ 271 at -1 in the infrared spectrum was not observed. Mass spectrum: 1560 cm m/e 472 (ll%,

MI),

395 (100, C6F,GePh,f),

(55, Ph3Ge+),

247 (100. Ph,GeF+),

228’(28,

318 (50, C6F5GePhf),

305

Ph2Gef).

4-Ethcxy-2,3,5

c6-tetrafluoroohenyltiphenylaermane

(nc) .

Elution with light

petrol/acetone

(9: 1 v/v) gave three prominent bands,

which were extracted

with acetone;

The fastest

moving band was tetraphenylgermane,

m.p.

22S”,

:

8.3 wt. [36(c)] m.p.

233L-440(infrared identification

was a mixture of bis (triphenylgermanium) of the authentic (CDC13):

compound)

1..41 (t, L 7 Hz,

The second band

[371).

oxfde. (infrared

and the rewired

compound.

3H, OCH2CIi3),

4.32

identical- with that

pMR

(q, L 7 Hz.

sp-

2H. OCl&CH3),

ca.

7.4 (m, >> 15H, Ph of both ‘he required compound and the germoxane) 19 spectrum (CDCf3) : 124.5 (m, 2F, F 2,6)), 156.3 Cm, p. p.m. F NMR 2P, P 3,s)

The third band was the gerrrkane

p.p.m.

1,2,4,5-TetrafIuoro-3,6-bis acetone/light

petrol

with acetone.

(infrared

identification).

The fastest-movLng The second

“F

NhIR

(CDC13):

(m, F 2,6 of Ph3Ge-R-HC6z4),

138.4

, the last two resonances.

was the germoxane

identification).

Elution with which were

band was tetraphenylgermane

band was a mixture of the required

spectrum

p.p.m,

fnc).

triphenyl-2,3,5,6-tetrafluorophenttlqermane

germoxane . 123.6

(triohenylaennyl)benzene

(I:4 v/v) gave three prominent bands,

extracted

comwtrnd,

(infrared

having

(nc) , and the

122.6

(s, C6E4(GePh3)2),

(m, F 3,5 of Ph3Ge-R-HC6E4)

equal intensities.

The third band

(infrared identification).

Aclaowledqment We are grateful

to Prof.

J. M.

Miller,

the mass s_pectra, and to the Australian

Brock University,

Research

Canada

Grants Committee

for

for

sup-port.

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