Conversion of [Pt(SRf)2(PPh2-n(C6F 5)n+1)2] (n = 0 or 1, Rf=C6HF 4-4) through carbon-fluorine bond activation to [Pt(SRf)2(1,2-C6F4(SRf)-(PPh2))] and chiral [Pt(SRf)2(1,2-C6F4(SRf)(PPh(C6F5)))]

Article abstract of DOI:10.1039/b407328b

Treatment of trans-[PtCl₂(PPh_2-n(C₆F ₅)_n+1)₂] (n = 0 or 1) with Pb(SC ₆HF₄-4)₂ yields a mixture of monometallic cis/trans [Pt(SC₆HF₄-4)₂(PPh _2-n(C₆F₅)_n+1)₂], thiolate-bridged bimetallic cis/trans [Pt₂(μ-SC₆HF ₄-4)₂(SC₆HF₄-4)₂(PPh _2-n(C₆F₅)_n+1)₂] and [Pt(SC₆HF₄-4)₂(1,2-C₆F ₄(SC₆HF₄-4)-(PPh_2-n(C ₆F₅)_n)].

Full text of DOI:10.1039/b407328b

Conversion of [Pt(SRf)2(PPh2 2 n(C6F5)n + 1)2] ( n = 0 or 1, RfNC6HF4-4)
through carbon–fluorine bond activation to
[Pt(SRf)2(1,2-C6F4(SRf)-(PPh2))] and chiral
[Pt(SRf)2(1,2-C6F4(SRf)(PPh(C6F5)))]†
Luis Villanueva,a Maribel Arroyo,b Sylvain Bernèsb and Hugo Torrens*a
a Facultad de Química, UNAM, Cd. Universitaria, 04510 México D.F., Mexico.
E-mail: torrens@servidor.unam.mx
b Centro de Química, Instituto de Ciencias, Benemerita UniversidadAutonoma de Puebla, Blvd. 14 Sur 6303,
San Manuel, 72570 Puebla, Puebla, Mexico
Received (in Cambridge, UK) 14th May 2004, Accepted 23rd June 2004
First published as an Advance Article on the web 30th July 2004
Treatment of trans-[PtCl2(PPh2 2 n(C6F5)n + 1)2] (n = 0 or 1)
with Pb(SC6HF4-4)2 yields a mixture of monometallic cis/trans
[Pt(SC6HF4-4)2(PPh2 2 n(C6F5)n + 1)2], thiolate-bridged bime-
As above, on standing as acetone solutions at room temperature,
neither pure cis or trans [Pt2(m-SC6HF4-4)2(SC6HF4-
4)2(PPh2(C6F5))2] (3, 4) nor cis or trans [Pt2(m-SC6HF4-
4)2(SC6HF4-4)2(PPh(C6F5)2)2] (8, 9) transform into each other
unless the corresponding free phosphine is present in the reaction
medium.
tallic
(C6F5)n + 1)2]
(PPh2 2 n(C6F5)n)].
cis/trans
[Pt2(m-SC6HF4-4)2(SC6HF4-4)2(PPh2 2 n
-
and
[Pt(SC6HF4-4)2(1,2-C6F4(SC6HF4-4)-
[Pt2(m-SC6HF4-4)2(SC6HF4-4)2(PPh2(C6F5))2] and [Pt2(m-
SC6HF4-4)2(SC6HF4-4)2(PPh(C6F5)2)2] evolve with intramolecu-
lar formation of the new ligands 2-(4-tetrafluorophenylthio)-
3,4,5,6-tetrafluorophenyldiphenylphosphine and 2-(4-tetrafluoro-
phenylthio)-3,4,5,6-tetrafluorophenylphenylpentafluorophenyl-
phosphine giving rise to the complexes [Pt(SC6HF4-4)2(1,2-C6F4-
The metal assisted functionalization of fluorinated hydrocarbons
has been an area of intense study during the last decade. Several
reports of carbon–fluorine bond activation have been published1
and there are also a number of structural determinations of
transition metal complexes with C–F?M interactions.2 The subject
has been reviewed.3
Previously,
we
have
reported
the
synthesis
of
[M(SC6F5)3(PMe2Ph)2] (M = Ru, Os), showing by X-ray diffrac-
tion that both compounds bear a C–F?M interaction in the solid
state.4 Following this interest, we have extended our work to
include fluorinated phosphine containing platinum complexes.
Although platinum derivatives of fluorinated phosphines are well
know, very few examples of carbon–fluorine bond activation at
platinum centres are known5,6 and none of these studies include
fluorothio-substituents.
Treatment of trans-[PtCl2(PPh2(C6F5))2] with Pb(SC6HF4-4)2 in
acetone at room temperature yields a complex equilibrium mixture
of monometallic cis and trans [Pt(SC6HF4-4)2(PPh2(C6F5))2] (cis
1, trans 2), thiolate bridged bimetallic cis and trans [Pt2(m-SC6HF4-
4)2(SC6HF4-4)2(PPh2(C6F5))2] (cis 3, trans 4) and [Pt(SC6HF4-
4)2(1,2-C6F4(SC6HF4-4)(PPh2))] 5, which can be isolated as yellow
diamagnetic crystalline solids. A similar reaction with trans-
[PtCl2(PPh(C6F5)2)2] affords cis and trans [Pt(SC6HF4-
4)2(PPh(C6F5)2)2] (cis 6, trans 7), cis and trans [Pt2(m-SC6HF4-
4)2(SC6HF4-4)2(PPh(C6F5)2)2] (cis 8, trans 9) and the chiral
complex [Pt(SC6HF4-4)2(1,2-C6F4(SC6HF4-4)(PPh–(C6F5))] 10.
Both reactions also freed the corresponding fluorophosphine
ligand.
Scheme 1 R2 = Ph2 or Ph(C6F5), R3 = Ph2(C6F5) or Ph(C6F5)2.
On standing as acetone solutions at room temperature, none of
the pure complexes trans-[Pt(SC6HF4-4)2(PPh2(C6F5))2] 2 or
trans-[Pt(SC6HF4-4)2(PPh(C6F5)2)2] 7 give rise to the related cis
isomer unless the corresponding free phosphine is present in the
reaction medium. Therefore, formation of the thiolate bridged
bimetallic compounds probably stems from compounds 2 and 7, a
reaction that liberates the fluorophosphine which, in turn, promotes
the cis–trans isomerization, affording compounds 1 and 6 as shown
in Scheme 1.
Examples of both, cis and trans monometallic fluorophosphines
containing Pt(II) complexes have been structurally characterized
previously7 but, to our knowledge, no member of the thiolate-
bridged family with fluorophosphines has been structurally studied
before. The molecular structure of 8 is shown in Fig. 1.‡
Fig. 1 Structure of cis-[Pt2(m-SC6HF4-4)2(SC6HF4-4)2(PPh(C6F5)2)2] 8. H
atoms are omitted for clarity and A labelled atoms are generated through the
symmetry x, y, 2z + 1/2. Principal bond dimensions (Å and °): Pt1–P1
2.268(3), Pt1–S1 2.327(3), Pt1–S2 2.359(2), Pt1–S3 2.370(2), P1–Pt1–S1
86.44(11), P1–Pt1–S2 98.65(10), S1–Pt1–S2 174.71(10), S1–Pt1–S3
93.83(10), S2–Pt1–S3 81.13(9).
† Electronic Supplementary Information (ESI) available: experimental
procedures and spectral data for all new compounds and crystallographic
data for 5, 8 and 10. http://www.rsc.org/suppdata/cc/b4/b407328b/
1942
C h e m . C o m m u n . , 2 0 0 4 , 1 9 4 2 – 1 9 4 3
T h i s j o u r n a l i s © T h e R o y a l S o c i e t y o f C h e m i s t r y 2 0 0 4

(SC6HF4-4)(PPh2))] 5 and a racemic mixture of [Pt(SC6HF4-
4)2(1,2-C6F4(SC6HF4)(PPh(C6F5))] 10 which have been structur-
ally characterized as shown in Figs. 2 and 3. For 10 a racemic
mixture was crystallized.
Although the ligands 1,2-C6F4(SMe)(PPh2), (1,2-C6F4–
(SMe))2(PPh) and 1,2-C6H4(SMe)(P(C6F5)2) are known,8 com-
plexes 5 and 10 are rare examples of metal promoted C–F activation
from PPh3 2 n(C6F5)n (n = 1 or 2) involving polyfluorothiolate
ligands to afford 1-thiolate-2-phosphine–tetrafluorophenyl com-
plexes.
Unfortunately, to date we have been unable to detect the freed
fluorine atom or any other fluorine containing species using either
mass spectrometry or 19F NMR (Pt–F, 2200 < d < 2300
ppm).9
To rationalize the outcome from these reactions, activation and
cleavage of an ortho carbon–fluorine bond at a phosphine ligand,
transfer of a thiolate moiety and rearrangement of the parent
bimetallic complexes have to be considered. A related reaction6 is
centres of a nucleophilic attack by a thiolate-sulfur atom.
Nucleophilic displacement of ortho-fluorine from polyfluorinated
aromatic ligands attached to transition metals has been observed in
a few examples where the C6F5 ring is bound to carbon or
phosphorus atoms.3
Notes and references
‡ Crystal data. Bruker P4 diffractometer, Mo–Ka (l = 0.71073 Å),
operated at room temp. 8: C60H14F36P2Pt2S4, MW = 1999.07, hexagonal,
P63/m, a = b = 25.675(2), c = 19.115(2), Z = 6, Dcalcd = 1.825 g cm23
.
R1 = 0.0542 for 3631 I > 2s(I) and wR = 0.1528 for 6577 data, 502
parameters and 28 restraints. 5: C36H13F16PPtS3, MW = 1071.70, triclinic,
¯
P1, a = 11.945(3), b = 12.0754(14), c = 13.4898(18), a = 102.108(10),
b = 102.397(17), g = 105.499(14), Z = 2, Dcalcd = 2.027 g cm23. R1 =
0.0431 for 4627 I > 2s(I) and wR = 0.1023 for 6109 data and 514
¯
parameters. 10: C36H8F21PPtS3, MW
=
1161.66, triclinic, P1, a
=
11.8338(10), b = 12.4575(14), c = 14.5848(13), a = 96.898(8), b =
107.898(7), g = 105.595(7), Z = 2, Dcalcd = 2.007 g cm23. R1 = 0.0348
for 5688 I > 2s(I) and wR = 0.0849 for 6727 data and 559 parameters.
CCDC 239571–239573. See http://www.rsc.org/suppdata/cc/b4/b407328b/
for crystallographic data in .cif or other electronic format.
the
formation
of
the
oxocarboplatinum
[PtMe(2-
OC6F4PPh2)(PPh2(C6F5))] from moist [PtMe(THF)(PPh2–
(C6F5))2]. An Ar–F?Pt interaction is expected to induce an
activated ortho-C–F bond bearing an electrophilic carbon atom.
Such interactions are known to render C–F bonds highly suscepti-
ble to nucleophilic attack.3 Therefore the ortho-carbon atoms C1 of
complexes 5 and 10—Figs. 2 and 3—can be envisaged as the
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Fig. 2 Structure of [Pt(SC6HF4-4)2(1,2-C6F4(SC6HF4-4)(PPh2))] 5. H
atoms are omitted for clarity. Principal bond dimensions (Å and °): Pt1–P1
2.261(2), Pt1–S1 2.268(2), Pt1–S2 2.300(2), Pt1–S3 2.378(2), S1–Pt1–P1
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Fig. 3 Structure of [Pt(SC6HF4-4)2(1,2-C6F4(SC6HF4-4)(PPh(C6F5))] 10. H
atoms are omitted for clarity. Principal bond dimensions (Å and °): Pt1–P1
2.2313(14), Pt1–S1 2.2812(14), Pt1–S2 2.3064(15), Pt1–S3 2.3537(14),
S1–Pt1–P1 89.41(5), S2–Pt1–P3 96.74(5).
C h e m . C o m m u n . , 2 0 0 4 , 1 9 4 2 – 1 9 4 3
1943