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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.
References
1.
G. B. Deacon, J_ Fluorine
2.
G.
3.
E. MuHer Vol.
G. J. Farquharson,
Chem.,
B. Deacon,
13 (2b),
8 (1976) 545.
Organometal.
(Ed.),
c-.
P. &r-tori and H. Adelt,
3.
P. Sartori and H.
6.
M _ W,
J. Fluorine 7.
G.
Chem., G.
Aust . J. Chem.,
J. Fluorine Chem.
Mobbs,
Rev.,
Methoden
Stuttgart,
J. Frohn,
R. Y,
B. Deacon,
Chem.
Houben-Weyl’s
G. Thieme.
Buxton,
and R. J- Phillips,
Sect. A,
J. Farquharson,
Chemie,
1974, PP. 114-120. Chem. , 3 (1973/l 974) 275. Ber.,
107 0 974) 1195.
and D. E.. M.
1 (1971/1972)
5 (1970) 355.
der Organischen
Watton,
179. and J. M.
Miller,
in press.
8.
G. 3. Deacon
9.
P. G. Cookson,
and P. W. G.
Felder,
Aust . J_ Chem.,
27 (1974) 1895.
B. Deacon,
Aust. P. W.
J. Chem., Felder,
23 (1970) 1359.
and G. J. Farquharson,
.
89 10,
.-R. A,
Cummins,
-24 (197lj 11.
M.
G.
P. Dunn,
and D. Oldfield,
f. Chem.,
2257,
Voronkov,
R. G: Mirskov,
L. v. .SkochiIova,
Dokl.
-193 [Chem:Abstr.,
and 4th, 2 0 972)
79 (1973) 78903x1.
G. B. Deacon,
Aust.
13.
B. F. E. Ford and J. R. Sams, and reference.s
V. G. Chemova,
Konf. Khim. Atsetilena,
Vses.
12.
14.
Aust.
J. Chem.,
20 0967)
459.
J. Organometal.
Chem.,
31 (1971) 47,
therein.
G. B, Deacon
and J. H. S. Green,
Spectrochim.
Acta,
Sect.
A,
and J. H.
Spectrochim.
Acta,
Sect. A, 24
24. (1968) 885. 15.
G. B. Deacon
S. Green,
(1968) 1125. 16.
T. Chivers,
G. F. Lanthier,
and J. M.
Miller,
J. Chem.
Sot.
A,
(1971) 2556. 17.
M _ I. Bruce, B, A. W.
J. Chem.
Coller,
Sot.
A (1968) 1459;
G. B. Deacon,
5 (1975) 335 and references 18.
W.
T. Reichle,
19.
R. C.
Poller,
20.
5. C.
Cohen
21.
MI
Spectrochim.
23.
K. M.
24.
R. D.
Mackay,
Acta,
Chambers
andT.
Pohlmann,
J. Burden,
Chem.,
J. Org.
Ber.,
Chem.
6 (1970) 83.
Chem. , 38 (1973) 319,
101 (1968) 2004.
and W.
Chivers,
C. Young,
Spectrochim.
Acta,
Sot.
G. Tesi,
(1964) 4782.
.
and R. E. Donadio,
20b (1965) 1. C.
R. Marsh,
and J. C. Tatlow,
22 (1966) 1183.
D. E. Fenton,
A. G. Massey,
J. Organometal.
28. 29.
N. K. Hota and C. J. Willis,
30.
K_ Nakamoto,
Weidenbruch,
I&ared
NewYork,
and D.
S. Urch,
6 (1966) 352,
Chem.,
P. Sartori and M.
B. Kushlefsky,
J. Chem.
F. E. Brinckman,
P. L. Coe,
. Tetrahedron,
31.
Fluorine
A, 24 (1968) 611.
-J. L. W.
Wiley,
22 (1966) 935. Adv.
13. B. Sowerby,
Z. Naturforsch.,
27.
Chem.,
therein.
P. Sartori and A. Golloch,
26.
J. Fluorine
18 (1969) 105.
and M . C . Vander Zwan.
22.
25.
Chem.,
and A. G. Massey,
and references
Sect.
and I. K. Johnson,
therein.
J. Organometal.
S. Newman
R. J. Bertino,
Can.
Spe&ra
1963,
pp.
I. Simmons,
Chem.
Ber.,
J. Chem.,
of Inorganic
100 (1967) 2049.
46 (1958) 3921.
and Coordination
Compounds,
197-198. and A. Ross,
Inorg.
Chem.,
2 (1963) 187.
90 32.
C.
Tamborskf aG4.E.
33,
G. T. Morgan and H.
34.
J. M.
Birchall,
J_ Burdon, W,
Solo&i;-
J. -0rganonietal.
D, K. Dre&,
T, Clarke,
(1962) 4977. 35.
f.
C&em.,
Jr &em~~Scc..
and k. k.
Haszeldine.
(1925)
17 .P969)
TFfS:
i760.
f. Chem.
Sot.
.B. Hollyhead,
and J. C.
Tatlow,
J- &em_
Sot,
(1965)
6336. 36.
G. E. Coates, 3rd Edn.,
37.
M.
M.
Methuen;
L. H.
Green,
London,
and K. Wade,
1967,
G. Henry and J. G. Noltes,
(a) p. 419;
J. +mer.
Chem.
Organometallic b) p_ 492: Sot.,
Com_pounds,
(c) p. 379.
82 (1960) 555.
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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