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A novel desulphination path to tris(polyfluorophenyl)thallium(III) compounds
Cl
Journal of Organometallic Chemish-y, 171 (1973) Cl-C4 0 ElsevierSequoia S-A., Lausanne- Printed in The Netherlands
Preliminary
communication
A NOVEL DESULPHINATION THALLIUM
G.
PATH TO TRIS(POLYFLUOROPHENYL)
(III) COMPOUNDS
B. Deacon
Chemistry
and R. J. Phillips
Department,
(Received
March
Monash
8th,
or g-HC6F4)
bromobis (polyfluorophenyl)
is difficult
(III) compounds, by reaction
with all reported The Grignard
preparation
(C 6Fs) 3Tl from (C 6Fs) 2TlEIr I 11 .
The recently
[ 31 syntheses
are limited
separation reported
of the air-sensitive
symmetrization
with two fluorines
[ 21
(III)
ortho to thallium,
thallium (III) cannot be obtained
by
We now report that tris (polyfluorophenyl)thallium(III)
compounds,
including
elimination
reactions.
acetatobis
of tris (pentafluorcphenyl)
of tris (polyfluorophenyl)thallium
to derivatives
e _ g. tris (2,3,4,5-tetrafluorophenyl) either method.
and barium or thallous
routes to tris (polyfluorophenyl)-
and involves
compounds
the corresponding
in pyridine.
to reproduce,
and decarboxylation
3168 (Australia)
R3Tl (R = C 6F5, R-HC 6F4,
between
thallium (III) derivatives
polyfluorobenzenesulphinates
thallium (III) compounds.
Victoria
1979)
have been prepared
There are problems
Clayton,
University,
Tris (polyfluorophenyl)thallium
thallium
-
@-HG 6F4) 3T1, can be formed by sulphur dioxide Few other Group 3B organometallics,
(polyfluorophenyl)thallium
and di-mesitylthallium(HI)
(III) compounds
compounds
viz.
some .
[ 43 , and some mcnc-
[ 51 have been obtained
by this
method. Reaction
of bromobis (polyfluorophenyl)thallium(III) or g-HC
compounds,
F ) , with either the corresponding
(R = C6F5,
R-IX6F4,
or thallous
polyfluorobenzenes6ulihinates,
(RS02)2Ba
R2T1Br barium
(R = C6F5 or R-HC6F4)
-
0.74 mm01
_
___
.._...
_“-.-_-__
10
30
10
10
.I_.
_
.
.._.
-C.l_--__.
30
180
120
so
Time (min.)
..._... ._.“_._____..-
...___._I____I__.__-...-.-
(2-IfC6F4)3Tl
f;e-SC6F4)3T’
@-HC6P4)$1
(C6F,J3Tl
*-..-_--
34
68
68
66
.--.-_-
(9)d
(60)
(38)c
(38)
a -_-_ -..-.IB___.._-___-_
p Crude &-HC6F4)3Tl(diox),
b Yields of recrystallized R3Tl(diox) complexes, obtained as described
c Sulphur dioxide (58%)was obtained in a similar experiment.
24% yield: Tl2SO4 Q. SO%)also formed,
in the text.
ml
19 F n.m,r. spectra of the reaction mixtures, on the assumption that no polyfluorophenyl
_-~_^_-_---*-,...-
0.49 mm01
g-HC6F4S02Tl
1.7 mm01
(e-HC$,SO,) 2Ba
0.29 mm01
@-HC6FqS02)2Ba
0.33 mm01
-.-..I”c.I-~I-.-.-- ___
groups were lost from the reaction mixture.
a Determined from the
l____.-._.-,_._
&HC6F4) 2TlBr )
3.1 mm01
‘(pHC6Fq)2TlBr
0.57 mm01
(E-HC~F~)2TlBr
0.49 mmoi
r ____...____,__..._ ^ .. .._-, . .
The Formation of Tris fpolyfluorophenyl)thallium OII) Compounds by Sulphur Dioxide Elimination Reactions ..____^._.^ _____“._.__ _,__-.__..,...”_,_.__.._ ._.. __“____ _^... _. . .... ._.__^.. “_._--.~_“..*__^-.- .-._.._ __..-_.._-_ ._.L_.. e,_.- _I_^_ ~_._. s..... ...“-___,_^_.^ ,..,._.,. % Yield Reaction Product Reactants C5H8N
TABLE1
c3 or G-EC 6F4S02T1, corresponding
in boiling
dry pyridine
tris (polyfluorophenyl)thallium(III),
2R2TlBr
t’
(RS02j2Ba
-
2R3Tl
(R = &HC
The products
were identified
spectra,
which were
isolated
After filtering
Sublimation
gave the corresponding complexes, points
in agreement
whilst
the new complex
BaBr2 +
reaction
mixtures,
contaminated
of the sublimates
These
(2)
by their 19F
mfxtures
coupling
constants,
R2T1Br
the oompounds
were
with R TlBr derivatives. 2 from 1,4-dioxan (diox)
(polyfluorophenyl)thallium(III)
had spectroscopic
with reported
Ij.
2 SO2
of the corresponding
the reaction complexes
cable
properties
and melting
data (R = C6F6 or R-HC6F4)
[ 2, 3, 61 ,
@-HC 6F4) 3Tl (dioxj , m . p. 238O (dec.) , was obtained 19 pure with a satisfactory F n.m.r. spectrum. The formation
analytically of thallous
sulphate
@able
from thermal decomposition reaction
f
by the thallium-fluorine
pure 1,4-dioxantris
R3Tl(diox) .
compounds
to_-HC 6F4) 3Tl c Tl~r f so2
than those
and crystallization
gave the
R-HC 6F4)
in the resulting
less
as crude pyridine
or
+
and in particular
significantly
derivatives.
problem was
1) during the preparation of the thallous
times in reaction
fluorophenyl)thallium
(:-HC
C6FS
6F4) 2TlBr f g-HC 6FpS02Tl
n.m.r.
under nitrogen
(1) (R = C6F5)
(III) pyridinates
encountered
of (o_-HC F ) Tl arises 643 sulphinate. Use of longer
and reaction
as unsublimable
with the latter reaction
(21 gave the tris(polyglues,
unless
and the same
an excess
of
6F4j2T1Br was used. Detection
eliminated
of sulphur dioxide
the possibility
that reactions
of bis (polyfluorophenyl)
(1) and (2) proceed
ation (4) of bis (polyfluorophenyl) though these
intermediates
R2TiBr +
M02SR
decomposition reaction
(1) _
(III) compounds .
(3) and desulphin-
OIIj complexes,
even
could not be isolated. R2T102SR + ----+=
MBr
R3Tl +
path (5) and (6) can be ruled out,
tetrafluorobenzenesulphinate
reaction
thallium (III) species
via formation
sulphinatothallium
-
R2T102SR The alternative
from a representative
that the tris (polyfluorophenyljtballium
were formed by rearrangement It is likely
in good yield
does not decompose
of the barium sulphinates
proceeds
(M = 4 Ba or TI) So2
(4)
since thallous by (5),
(3)
2,3,4,
S-
and thermal
too slowly
to be a step in
c4
M02sR
.-
R2TlBr -I-MR
MR
+
(5)
So2
.@A = SBa orT1) R3TL f MBr
+
(6)
Acknowledgement We
are gratefulto the Australian
Research Grants Committee for support.
References E. Brinkman, Z. Naturforsch, Teil B,
1.
J. w. L. PohlmannandF.
2.
G.
3.
G. B, DeaconandR.
J. Phillips,Aust.
4.
G. B. DeaconandI.
K. Johnson, J. FIuorineChem.,
5,
G. B. DeaconandI.
K. Johnson, J. Organometal. Chem.,
20 (1965) 5. B,
DeaconandD.
G. Vince,Aust. J. Chem,. J. Chem.,
28 (1975) 1931. 31 (1978) 1769. 6 (1975) 437.
112 (1976) 123. 6.
G. B, Deacon, R, M. 11 (1978) 57.
Slade, andD.
G. VinCe, J. Fluorine Chem.,
Journal of Organometallic Chemish-y, 171 (1973) Cl-C4 0 ElsevierSequoia S-A., Lausanne- Printed in The Netherlands
Preliminary
communication
A NOVEL DESULPHINATION THALLIUM
G.
PATH TO TRIS(POLYFLUOROPHENYL)
(III) COMPOUNDS
B. Deacon
Chemistry
and R. J. Phillips
Department,
(Received
March
Monash
8th,
or g-HC6F4)
bromobis (polyfluorophenyl)
is difficult
(III) compounds, by reaction
with all reported The Grignard
preparation
(C 6Fs) 3Tl from (C 6Fs) 2TlEIr I 11 .
The recently
[ 31 syntheses
are limited
separation reported
of the air-sensitive
symmetrization
with two fluorines
[ 21
(III)
ortho to thallium,
thallium (III) cannot be obtained
by
We now report that tris (polyfluorophenyl)thallium(III)
compounds,
including
elimination
reactions.
acetatobis
of tris (pentafluorcphenyl)
of tris (polyfluorophenyl)thallium
to derivatives
e _ g. tris (2,3,4,5-tetrafluorophenyl) either method.
and barium or thallous
routes to tris (polyfluorophenyl)-
and involves
compounds
the corresponding
in pyridine.
to reproduce,
and decarboxylation
3168 (Australia)
R3Tl (R = C 6F5, R-HC 6F4,
between
thallium (III) derivatives
polyfluorobenzenesulphinates
thallium (III) compounds.
Victoria
1979)
have been prepared
There are problems
Clayton,
University,
Tris (polyfluorophenyl)thallium
thallium
-
@-HG 6F4) 3T1, can be formed by sulphur dioxide Few other Group 3B organometallics,
(polyfluorophenyl)thallium
and di-mesitylthallium(HI)
(III) compounds
compounds
viz.
some .
[ 43 , and some mcnc-
[ 51 have been obtained
by this
method. Reaction
of bromobis (polyfluorophenyl)thallium(III) or g-HC
compounds,
F ) , with either the corresponding
(R = C6F5,
R-IX6F4,
or thallous
polyfluorobenzenes6ulihinates,
(RS02)2Ba
R2T1Br barium
(R = C6F5 or R-HC6F4)
-
0.74 mm01
_
___
.._...
_“-.-_-__
10
30
10
10
.I_.
_
.
.._.
-C.l_--__.
30
180
120
so
Time (min.)
..._... ._.“_._____..-
...___._I____I__.__-...-.-
(2-IfC6F4)3Tl
f;e-SC6F4)3T’
@-HC6P4)$1
(C6F,J3Tl
*-..-_--
34
68
68
66
.--.-_-
(9)d
(60)
(38)c
(38)
a -_-_ -..-.IB___.._-___-_
p Crude &-HC6F4)3Tl(diox),
b Yields of recrystallized R3Tl(diox) complexes, obtained as described
c Sulphur dioxide (58%)was obtained in a similar experiment.
24% yield: Tl2SO4 Q. SO%)also formed,
in the text.
ml
19 F n.m,r. spectra of the reaction mixtures, on the assumption that no polyfluorophenyl
_-~_^_-_---*-,...-
0.49 mm01
g-HC6F4S02Tl
1.7 mm01
(e-HC$,SO,) 2Ba
0.29 mm01
@-HC6FqS02)2Ba
0.33 mm01
-.-..I”c.I-~I-.-.-- ___
groups were lost from the reaction mixture.
a Determined from the
l____.-._.-,_._
&HC6F4) 2TlBr )
3.1 mm01
‘(pHC6Fq)2TlBr
0.57 mm01
(E-HC~F~)2TlBr
0.49 mmoi
r ____...____,__..._ ^ .. .._-, . .
The Formation of Tris fpolyfluorophenyl)thallium OII) Compounds by Sulphur Dioxide Elimination Reactions ..____^._.^ _____“._.__ _,__-.__..,...”_,_.__.._ ._.. __“____ _^... _. . .... ._.__^.. “_._--.~_“..*__^-.- .-._.._ __..-_.._-_ ._.L_.. e,_.- _I_^_ ~_._. s..... ...“-___,_^_.^ ,..,._.,. % Yield Reaction Product Reactants C5H8N
TABLE1
c3 or G-EC 6F4S02T1, corresponding
in boiling
dry pyridine
tris (polyfluorophenyl)thallium(III),
2R2TlBr
t’
(RS02j2Ba
-
2R3Tl
(R = &HC
The products
were identified
spectra,
which were
isolated
After filtering
Sublimation
gave the corresponding complexes, points
in agreement
whilst
the new complex
BaBr2 +
reaction
mixtures,
contaminated
of the sublimates
These
(2)
by their 19F
mfxtures
coupling
constants,
R2T1Br
the oompounds
were
with R TlBr derivatives. 2 from 1,4-dioxan (diox)
(polyfluorophenyl)thallium(III)
had spectroscopic
with reported
Ij.
2 SO2
of the corresponding
the reaction complexes
cable
properties
and melting
data (R = C6F6 or R-HC6F4)
[ 2, 3, 61 ,
@-HC 6F4) 3Tl (dioxj , m . p. 238O (dec.) , was obtained 19 pure with a satisfactory F n.m.r. spectrum. The formation
analytically of thallous
sulphate
@able
from thermal decomposition reaction
f
by the thallium-fluorine
pure 1,4-dioxantris
R3Tl(diox) .
compounds
to_-HC 6F4) 3Tl c Tl~r f so2
than those
and crystallization
gave the
R-HC 6F4)
in the resulting
less
as crude pyridine
or
+
and in particular
significantly
derivatives.
problem was
1) during the preparation of the thallous
times in reaction
fluorophenyl)thallium
(:-HC
C6FS
6F4) 2TlBr f g-HC 6FpS02Tl
n.m.r.
under nitrogen
(1) (R = C6F5)
(III) pyridinates
encountered
of (o_-HC F ) Tl arises 643 sulphinate. Use of longer
and reaction
as unsublimable
with the latter reaction
(21 gave the tris(polyglues,
unless
and the same
an excess
of
6F4j2T1Br was used. Detection
eliminated
of sulphur dioxide
the possibility
that reactions
of bis (polyfluorophenyl)
(1) and (2) proceed
ation (4) of bis (polyfluorophenyl) though these
intermediates
R2TiBr +
M02SR
decomposition reaction
(1) _
(III) compounds .
(3) and desulphin-
OIIj complexes,
even
could not be isolated. R2T102SR + ----+=
MBr
R3Tl +
path (5) and (6) can be ruled out,
tetrafluorobenzenesulphinate
reaction
thallium (III) species
via formation
sulphinatothallium
-
R2T102SR The alternative
from a representative
that the tris (polyfluorophenyljtballium
were formed by rearrangement It is likely
in good yield
does not decompose
of the barium sulphinates
proceeds
(M = 4 Ba or TI) So2
(4)
since thallous by (5),
(3)
2,3,4,
S-
and thermal
too slowly
to be a step in
c4
M02sR
.-
R2TlBr -I-MR
MR
+
(5)
So2
.@A = SBa orT1) R3TL f MBr
+
(6)
Acknowledgement We
are gratefulto the Australian
Research Grants Committee for support.
References E. Brinkman, Z. Naturforsch, Teil B,
1.
J. w. L. PohlmannandF.
2.
G.
3.
G. B, DeaconandR.
J. Phillips,Aust.
4.
G. B. DeaconandI.
K. Johnson, J. FIuorineChem.,
5,
G. B. DeaconandI.
K. Johnson, J. Organometal. Chem.,
20 (1965) 5. B,
DeaconandD.
G. Vince,Aust. J. Chem,. J. Chem.,
28 (1975) 1931. 31 (1978) 1769. 6 (1975) 437.
112 (1976) 123. 6.
G. B, Deacon, R, M. 11 (1978) 57.
Slade, andD.
G. VinCe, J. Fluorine Chem.,