Oxosulfido Complexes of Platinum - (Ph3P)2Pt(S 2O) and (Ph3P)4Pt2(μ-S)(μ-SO) - Their Formation and Properties

Article abstract of DOI:10.1002/ejic.200300348

The platinum S₂O complex [(Ph₃P)₂Pt(S ₂O)] (10) was obtained by S₂O transfer reactions from tetrathiolane 2-oxide (8), tetrathiolane 2,3-dioxide (5), and pentathiane 3-oxide (6) to [(C₂H₄)Pt(PPh₃)₂1] (4). The S₂O complex 10 further reacts with 4 to give a novel binuclear platinum complex 16, which is found to be a source of several platinum S_nO_m complexes. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.

Full text of DOI:10.1002/ejic.200300348

SHORT COMMUNICATION
Oxosulfido Complexes of Platinum — (Ph3P)2Pt(S2O) and
(Ph3P)4Pt2(µ-S)(µ-SO) — Their Formation and Properties
Akihiko Ishii,*[a] Masami Murata,[a] Hideaki Oshida,[a] Kimiyo Matsumoto,[a] and
Juzo Nakayama*[a]
Keywords: Platinum / S ligands / Oxo ligands
The platinum S2O complex [(Ph3P)2Pt(S2O)] (10) was ob-
tained by S2O transfer reactions from tetrathiolane 2-oxide
(8), tetrathiolane 2,3-dioxide (5), and pentathiane 3-oxide (6)
to [(C2H4)Pt(PPh3)2] (4). The S2O complex 10 further reacts
with 4 to give a novel binuclear platinum complex 16, which
is found to be a source of several platinum SnOm complexes.
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2003)
The coordination chemistry of organotransition metal which further reacted with 4 to yield the binuclear platinum
compounds of sulfur oxides has been attracting consider-
able attention.[1Ϫ4] Among them, disulfur monoxide (S2O)
complexes 1 of several transition metals (Nb,[5] Mo,[6]
Mn,[7Ϫ11] Re,[8] Rh,[2] Os,[12] Ir,[2,5,9,10,12,13] and Pt[14]) are
known, in which platinumϪS2O complexes 2 (E ϭ S, EЈ ϭ
SO) were reported very recently by Tokitoh and co-work-
ers.[14] They synthesized the platinumϪS2O and ϪSe2O
complexes, 2 by oxidation of the respective S2 and Se2 com-
plexes,[15] which were prepared for the first time by taking
advantage of bulky phosphane ligands (TbtMe2P and
BbtMe2P). Similarly, most of the other S2O complexes were
synthesized by oxidation of the corresponding S2 com-
plexes, and a few were prepared by S2O transfer reactions
from 4,5-diphenyl-3,6-dihydro-1,2-dithiin 1-oxide[6,9,10] or
reaction with S2O(THF)x.[2] On the other hand, the chemis-
try of sulfido complexes of platinum bearing the Pt2S2 core
(3) has also been drawing considerable interest.[16] Another
recent topic in this field is oxidative additions of Pt0 com-
plex 4 to a thiosulfinate [ϪSϪS(O)Ϫ] moiety in cyclic sulfur
compounds.[17Ϫ21] We have been studying the synthesis and
reactivities of cyclic polysulfides, and have reported on the
chemistry of tetrathiolane 2,3-dioxide (5),[22,23] pentathiane
3-oxide (6),[24,25] and S8O,[26] all of which act as S2O trans-
fer reagents.[27Ϫ30] Recently we also reported the reaction of
dithiirane 1-oxides 7 with 4.[31] Here, we report the reaction
of 5, 6, and tetrathiolane 2-oxide (8)[23] with 4, where an
S2O transfer took place giving rise to [(Ph3P)2Pt(S2O)]
complex [(Ph3P)4Pt2(µ-S)(µ-SO)].
Tetrathiolane 2-oxide (8), prepared in situ by oxidation
of tetrathiolane (9) with dimethyldioxirane (DMD)[32,33] at
Ϫ20 °C,[23] was allowed to react with two molar equivalents
of 4 in toluene at Ϫ20 °C to produce [(Ph3P)2Pt(S2O)] (10;
0.80 molar equiv.), [(Ph3P)2Pt(S3O)] (11; 0.19 molar
equiv.),[34] the dithiolato complex 12 (0.09 molar equiv.),
[(Ph3P)2Pt{(1-Ad)(tBu)CϭS}] (13; 0.31 molar equiv.),[31]
and (1-Ad)(tBu)CϭS (14; 0.47 molar equiv.) [Equation (1)].
[a]
Department of Chemistry, Faculty of Science,
Saitama University,
Sakura-ku, Saitama 338Ϫ8570, Japan
Fax: (internat.) ϩ81-48/858-3700
E-mail: ishiiaki@chem.saitama-u.ac.jp
Supporting information for this article is available on the
WWW under http://www.eurjic.org or from the author.
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DOI: 10.1002/ejic.200300348
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Oxosulfido Complexes of Platinum
SHORT COMMUNICATION
with only the set A. In the 31P NMR spectrum, two dou-
blets appear at δ ϭ 18.2 and 18.4 [2JP,P ϭ 7 Hz] with satel-
lite signals due to the 195Pt nucleus [1JPt,P ϭ 4364 and
3410 Hz in CDCl3, respectively]. These coupling constant
values are quite similar to those of the S2O complex 2
1
(Ar ϭ Bbt, E ϭ S, EЈ ϭ SO) [2JP,P ϭ 8, JPt,P ϭ 4263 and
3254 Hz].[14] Shaver reported that the S3O complex 11 can
be obtained by reaction of [(PPh3)2Pt(SH)2] with SO2,[34]
while we found that the reaction of S8O with 4 yields 11 in
good yield.[36]
(1)
The reaction of tetrathiolane 2,3-dioxide (5) with an equi-
molar amount of 4 yielded the S2O complex 10 (0.62 molar
equiv.) along with (1R*,3S*)- and (1R*,3R*)-dithiirane 1-
oxides (15)[22,23] (0.24 and 0.25 molar equiv., respectively)
and thioketone 14 (0.21 molar equiv.) [Equation (2)]. Inter-
estingly, when two molar equivalents of 4 were employed,
binuclear platinum complex 16 was obtained. Indeed, the
isolated S2O complex 10 reacted with 4 very quickly to give
16 in high yield [Equation (3)]. Insertion reactions of 4 into
the SϪS bond of cyclic oligosulfide oxides[17Ϫ21] and Fe2(µ-
The structure of the S2O complex 10 was determined by
X-ray crystallography (Figure 1).[35] The crystal contained
one molecule of benzene — the recrystallization solvent —
per two molecules of 10, and the Pt(S2O) moiety was dis-
ordered as shown in Figure 1a: the occupancies of the set
A [Pt(1A)S(1A)S(2A)O(1A)] and the set B [Pt(1B)S-
(1B)S(2B)O(1B)] were almost equivalent (0.515 and 0.485,
respectively). Figure 1b shows the whole of the molecule
[37]
S2)(CO)6 have been reported. The properties of complex
16 will be described later in this paper.
(2)
(3)
Similarly, pentathiane 3-oxide (6) was treated with 4 (2
molar equiv.) to furnish the S2O complex 10 and the dithi-
olato-thiolato complex 17 in 0.70 and 0.85 molar equiv.,
respectively [Equation (4)]. The structure of 17 was deter-
mined by X-ray crystallography (Figure 2).[35]
(4)
Interestingly, complex 17 decomposes in CDCl3 at 65 °C
(2 h) to give an alternative complex 18 (0.23 molar equiv.)
and tBu(Ph)CϭS (0.23 molar equiv.) [Equation (5)]. Com-
plex 18 exhibits a singlet at δ ϭ 22.7 (1JPt,P ϭ 3939 Hz) in
the 31P NMR spectrum of the mixture, and this 1JPt,P value
is quite similar to that of 2 (Ar ϭ Bbt, E ϭ EЈ ϭ S) (δ ϭ
Figure 1. ORTEP drawings of (Ph3P)2Pt(S2O) (10) (50% ellipsoidal
probability): (a) disorder of the Pt(S2O) moiety (phenyl groups are
omitted for clarity), set
A (0.515 occupancy) Pt(1A)S(1A)-
S(2A)O(1A), set B (0.485 occupancy) Pt(1B)S(1B)S(2B)O(1B); (b)
1
the whole of 10 drawn with the set A
Ϫ32.2 ppm, JPt,P ϭ 3909 Hz).[15] Thus, we tentatively as-
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SHORT COMMUNICATION
We tried to prepare the binuclear platinum complex 16
by oxidation of [(Ph3P)2Pt]2(µ-S)2 (3: L ϭ PPh3).[39] It has
been reported that oxidation of a binuclear platinum com-
plex bridged by S gives the µ-SO complex.[40] However, 16
was not obtained because of the insolubility of
[(Ph3P)2Pt]2(µ-S)2 in the usual organic solvents. Complex 16
decomposes upon heating at 50 °C in CDCl3 to yield the
S2O complex 10, the S2O2 complex 20,[41] and
[(PPh3)2PtCl2] [Equation (7)]. The identification of the S2O2
complex 20 was done by comparison of the 31P NMR spec-
trum of an authentic sample prepared by the reported
method.[41] The decomposition in the presence of (1-
Ad)(tBu)CϭS (14) in PhH yielded the thioketone complex
13 and the S2O complex 10 as the main products in 0.66
and 0.61 molar equiv., respectively, along with the S2O2
complex 20 and recovered thioketone 14. The formation of
the thioketone complex 13 indicates the intervention of
(PPh3)2Pt.
Figure 2. Molecular structure of [(tBu)(Ph)CS3]Pt(PPh3)2 (17); hy-
˚
drogen atoms are omitted for clarity; selected bond lengths [A] and
(7)
angles [deg]: Pt(1)ϪP(1) 2.2854(19), Pt(1)ϪP(2) 2.297(3),
Pt(1)ϪS(3) 2.307(2), Pt(1)ϪS(1) 2.3350(18), S(1)ϪS(2) 2.061(4),
S(2)ϪC(37) 1.837(9), S(3)ϪC(37) 1.837(8); P(1)ϪPt(1)ϪP(2)
99.39(8), P(1)ϪPt(1)ϪS(3) 86.99(8), P(2)ϪPt(1)ϪS(3) 171.29(8),
P(1)ϪPt(1)ϪS(1) 174.65(9), P(2)ϪPt(1)ϪS(1) 84.32(8), S(3)Ϫ
Pt(1)ϪS(1) 89.74(8), S(2)ϪS(1)ϪPt(1) 106.27(12), C(37)Ϫ
S(2)ϪS(1) 100.5(3), C(37)ϪS(3)ϪPt(1) 103.6(3), C(7)ϪP(1)ϪPt(1)
114.7(3), C(13)ϪP(1)ϪPt(1) 111.5(3), C(1)ϪP(1)ϪPt(1) 115.4(3),
C(31)ϪP(2)ϪPt(1) 112.7(4), C(25)ϪP(2)ϪPt(1) 112.4(3), C(19)Ϫ
P(2)ϪPt(1) 120.3(3), S(2)ϪC(37)ϪS(3) 105.3(5), C(42)Ϫ
C(37)ϪC(38) 112.1(8)
A plausible mechanism for the thermal decomposition of
16 is depicted in Scheme 1. Initially, 16 decomposes via two
pathways: in Path A, it extrudes (PPh3)2Pt, which is trapped
by thioketone 14 to yield 13, to give the S2O complex 10; in
Path B, 16 splits into the SO complex 21 and [(PPh3)2Pt(S)].
Lorenz and Kull have reported that an attempt to prepare
the SO complex 21 by thermolysis of the episulfoxide com-
plex 22 results in the formation of the S2O2 complex 20.[41]
We propose that the SO complex 21 dimerizes to give an-
other binuclear platinum complex 23 that readily extrudes
(PPh3)2Pt to furnish the S2O2 complex 20. This proposal is
strongly supported by the fact that oxidation of 16 with
signed the S2 complex structure 18 to this compound. How-
ever, the complex was not stable enough to be isolated; pro-
longed heating of the mixture or even allowing it to stand
at room temperature for several hours led to complete dis-
appearance of the signal. We also examined the reaction
of tetrathiolane 9 with 4. The reaction yielded mainly the
dithiolato complex 12 and the thioketone complex 13. In
addition, 31P NMR spectroscopy showed a small signal due
to 18 [Equation (6)]. The dithiolato complex 12 was also
formed by the reaction of dithiirane 19 with 4 in benzene.[38]
(5)
(6)
Scheme 1. Plausible mechanism for reactions of the platinum di-
nuclear complex 16
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Oxosulfido Complexes of Platinum
SHORT COMMUNICATION
7.23 (t, J ϭ 7.0 Hz, 6 H), 7.44Ϫ7.49 (m, 12 H) ppm. 31P NMR
DMD yields the S2O2 complex 20 in high yield, probably
via 23. The fate of [(PPh3)2Pt(S)] is unclear, but the forma-
tion of [(PPh3)2PtCl2] upon thermolysis in CDCl3 implies
the formation of [(Ph3P)2Pt]2(µ-S)2 (3: L ϭ PPh3), which
reportedly reacts with CH2Cl2 to give [(PPh3)2PtCl2].[16] Ir-
radiation of 16 with light in CDCl3 gave the S2O2 complex
20, [PtCl2(PPh3)2], and Ph3PϭX (X ϭ O, S) indicating that
Path B is dominant in the photolysis.
1
(162 MHz,CDCl3): δ ϭ 22.9 (s, JPt,P ϭ 2925 Hz) ppm. FAB MS
(m-nitrobenzyl alcohol): m/z
ϭ ϩ 1], 931, 853.
989 [Mϩ
C51H54P2PtS2 (988.14): calcd. C 61.99, H, 5.51; found C 62.00, H
5.62.
Reaction of Tetrathiolane 2,3-Dioxide 5 with 4
Equimolar Amount of 4: Compound 4 (20.7 mg, 0.0277 mmol) was
added to a solution of 5 (10.1 mg, 0.0277 mmol) in toluene (1 mL)
at Ϫ20 °C under argon. The mixture was stirred for 1 h at this
temperature and the solvent was then evaporated to dryness. The
residue was subjected to column chromatography (silica gel,
CH2Cl2/Et2O, 5:1) to give a mixture of thioketone 14 and the
(1R*,3R*)- and (1R*,3S*)-dithiirane 1-oxides 15, and the S2O com-
plex 10 (13.8 mg, 0.62 molar equiv.). The mixture of 14 and 15 was
further subjected to HPLC (silica gel, CH2Cl2/hexane 1:1) to give
the thioketone 14 (1.4 mg, 0.21 molar equiv.), (1R*,3R*)-dithiirane
1-oxide [(1R*,3R*)-15; 1.9 mg, 0.24 molar equiv.], and (1R*,3S*)-
dithiirane 1-oxide [(1R*,3S*)-15; 2.0 mg, 0.25 molar equiv.].
In summary, the platinum S2O complex 10 was obtained
by S2O transfer reactions from tetrathiolane 2-oxide (8),
tetrathiolane 2,3-dioxide (5) and pentathiane 3-oxide (6) to
[(PPh3)2Pt(C2H4)] (4). The S2O complex 10 further reacts
with 4 to give a novel binuclear platinum complex 16, which
is found to be a source of several platinumϪSnOm com-
plexes.
Two Molar Equivalents of 4: Tetrathiolane 9 (10 mg, 0.031 mmol)
was oxidized with four molar equivalents of DMD (0.102 ,
1.2 mL, 0.123 mmol) in dichloromethane (1.5 mL) for 1 h at Ϫ20
°C. The solvent was removed under reduced pressure below Ϫ20
°C, and the resulting tetrathiolane 2,3-dioxide 5 was used without
further purification. The 2,3-dioxide 5 was dissolved in toluene
(2 mL) at Ϫ20 °C, and the solution was treated with a solution of
4 (45 mg, 0.060 mmol) in toluene (2 mL) at this temperature. The
solution turned immediately from colorless to deep yellow and was
stirred for 10 min at Ϫ20 °C. Removal of the solvent under reduced
pressure gave an orange residue, the 31P NMR integral ratio of
which indicated the formation of the thioketone complex 13,
[(PPh3)4Pt2-(µ-S)(µ-SO)] (16), the S2O complex 10, and the S-ox-
ides of 12[31] in the molar ratio of 26:13:29:32, along with Ph3Pϭ
O and Ph3PϭS. The molar ratio was obtained based on the 31P
NMR integral ratio. The S-oxides of 12 are considered to be
formed by reactions of dithiirane 1-oxides 15 with 4.[31] The bi-
nuclear platinum complex 16 could not isolated in this experiment
because it was not eluted from the silica-gel column.
Experimental Section
Reaction of Tetrathiolane 2-Oxide (8) with 4: An acetone solution
of DMD (0.106 , 0.30 mL, 0.032 mmol) was added to a solution
of tetrathiolane 9 (10 mg, 0.031 mmol) in CH2Cl2 (2 mL) at Ϫ20
°C under argon. The mixture was stirred for 1 h at this temperature
and then the solvent was removed in vacuo below Ϫ20 °C. The
residue was dissolved in toluene (1 mL) at Ϫ20 °C and then treated
with a solution of [(PPh3)2Pt(C2H4)] (4; 48 mg, 0.062 mmol) in
toluene (2 mL). After stirring for 10 min, the solvent was evapo-
rated to dryness and the residue was subjected to column chroma-
tography (silica gel, CH2Cl2/Et2O, 5:1) to elute first a mixture of 1-
adamantyl tert-butyl thioketone (14), the dithiolato complex (12),
and [(PPh3)2Pt{(1-Ad)(tBu)CϭS}] (13) and then [(PPh3)2Pt(S3O)]
(11; 4.9 mg, 0.19 molar equiv.) and [(PPh3)2Pt(S2O)] (10; 19.7 mg,
0.80 molar equiv.) in this order. The mixture of 12, 13, and 14 was
further subjected to gel permeation chromatography (GPC) with
CHCl3 as solvent to give a mixture (12.8 mg) of 12 (0.09 molar
equiv.) and 13 (0.31 molar equiv.), and 1-adamantyl tert-butyl
thioketone (14; 3.5 mg, 0.47 molar equiv.). The yields of 12 and 13
were estimated on the basis of the 1H NMR integral ratio. The
crude S2O complex 10 was precipitated from a mixed solvent of
dichloromethane and hexane, and the collected powder was washed
with benzene several times to give the analytical sample. When the
reaction was conducted using four molar equivalents of 4, the
thioketone complex 13 was not formed and the dithiolato complex
12 was isolated in nearly pure form after chromatographic purifi-
cation. The crude dithiolato complex 12 was washed with ethanol
several times to give the analytical sample.
Reaction of the S2O Complex 10 with 4: A solution of 4 (21.7 mg,
0.029 mmol) in toluene (1.5 mL) was added at 0 °C to a solution
of 10 (23.2 mg, 0.029 mmol) in toluene (1.5 mL) under argon. The
mixture was stirred for 1 h at 0 °C, and the solution was concen-
trated to ca. one-fourth of its original volume under reduced press-
ure. Diethyl ether was added to precipitate the product, and the
resulting precipitates were collected by filtration to give 47.7 mg
(0.71 molar equiv.) of [(PPh3)4Pt2(µ-S)(µ-SO)] (16).
16: Yellow powder, m.p. 179 °C (dec.). 1H NMR (400 MHz,
CDCl3): δ ϭ 6.97Ϫ7.02 (m, 24 H), 7.11Ϫ7.18 (m, 12 H), 7.29Ϫ7.34
(m, 12 H), 7.47Ϫ7.52 (m, 12 H) ppm. 31P NMR (CDCl3,
1
1
162 MHz): δ ϭ 21.0 (m, JPt,P ϭ 3394 Hz), 21.8 (m, JPt,P
ϭ
2427 Hz) ppm. IR (KBr): ν˜ ϭ 1095 cmϪ1. ESI MS: m/z ϭ 1519.2
[Mϩ ϩ 1]. C72H60OP4Pt2S2 (1519.44): calcd. C 56.91, H 3.98; found
C 56.13, H 3.94.
10: Yellow powder, m.p. 200 °C (dec.). 1H NMR (400 MHz,
CDCl3): δ ϭ 7.15Ϫ7.23 (m, 12 H), 7.28Ϫ7.36 (m, 18 H) ppm. 31P
Reaction of Pentathiane 3-Oxide 6 with 4: A solution of 4 (84 mg,
0.113 mmol) in toluene (12 mL) was added over 15 min to a solu-
NMR (162 MHz, CDCl3): δ ϭ 18.2 (d, 2JP,P ϭ 7, 1JPt,P ϭ 4364 Hz), tion of 6 (18 mg, 0.056 mmol) in toluene (2 mL) at Ϫ15 °C. The
18.4 (d, 2JP,P ϭ 7, 1JPt,P ϭ 3409 Hz) ppm. FAB MS (m-nitrobenzyl
alcohol): m/z ϭ 800 [Mϩ ϩ 1], 719. C36H30OP2PtS2 (799.78): calcd.
C 54.06, H 3.78; found C 53.58, H, 3.54.
solvent was removed under reduced pressure, and the residue was
subjected to column chromatography (silica gel, CHCl3 and then
CH2Cl2/Et2O 4:1) to give [(tBu)(Ph)CS3]Pt(PPh3)2 (17; 46 mg, 0.85
12: Off-white powder, m.p. 225Ϫ226 °C (dec.). 1H NMR molar equiv.) and the S2O complex 10 (31.3 mg, 0.70 molar equiv.).
(400 MHz, CDCl3): δ ϭ 1.20Ϫ1.40 (m, 9 H), 1.52Ϫ1.68 (m, 6 H),
1.94 (br. s, 3 H), 2.21 (br. s, 6 H), 7.14 (t, J ϭ 7.0 Hz, 12 H),
17: Yellow crystals, m.p. 143Ϫ147 °C (dec.) (CHCl3/EtOH). 1H
NMR (CDCl3, 400 MHz): δ ϭ 1.11 (s, 9 H), 6.95Ϫ7.01 (m, 6 H),
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SHORT COMMUNICATION
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7.03Ϫ7.09 (m, 6 H), 7.14Ϫ7.19 (m, 8 H), 7.26Ϫ7.38 (m, 7 H),
7.48Ϫ7.54 (m, 6 H), 8.08Ϫ8.11 (m, 2 H) ppm. 31P NMR
2
1
(162 MHz, CDCl3): δ ϭ 18.5 (d, JP,P ϭ 23, JPt,P ϭ 2754 Hz),
2
1
22.9 (d, JP,P ϭ 23, JPt,P ϭ 3057 Hz) ppm. C47H44P2PtS3·2CHCl3
(C49H46Cl6P2PtS3; 1200.80): calcd. C 49.01, H 3.86; found C 49.06,
H 3.75.
[8]
[9]
Reaction of Tetrathiolane
9 with 4: Compound 4 (6.1 mg,
0.0081 mmol) was added at room temperature to a solution of 9
(2.7 mg, 0.0081 mmol) in benzene (2 mL). The yellow mixture was
stirred for 15 min at room temperature, and the solvent was re-
moved under reduced pressure. The 31P NMR spectrum of the resi-
due indicated the formation of the dithiolato complex 12, the
thioketone complex 13, and a compound assigned tentatively to
[10]
[11]
[12]
[13]
[14]
[15]
[16]
1
the S2 complex 18 (δ ϭ 22.7 ppm, JPt,P ϭ 3939 Hz) in the molar
ratio of 32:57:11.
Thermal Decomposition of 16. In CDCl3: A solution of 16 (10 mg,
0.0065 mmol) in CDCl3 (4 mL) under argon was heated at 50 °C
for 1.5 h. The 31P NMR spectrum of an aliquot taken from the
mixture indicated the formation of the S2O complex 10, the S2O2
[17]
[18]
1
complex 20 (δ ϭ 6.4, JPt,P ϭ 4019 Hz), [(PPh3)2PtCl2] (δ ϭ 14.9,
1JPt,P ϭ 3672 Hz), 16, Ph3PϭS (δ ϭ 44.0 ppm), and Ph3PϭO (δ ϭ
29.8 ppm) in the molar ratio of 33:11:21:11:14:11.
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]
In Benzene in the Presence of Thioketone 14: A solution of 16
(23 mg, 0.015 mmol) and 14 (3.6 mg, 0.015 mmol) in benzene
(4.5 mL) was heated at 50 °C for 4 h under argon, and then the
solvent was removed under reduced pressure. The 31P NMR spec-
trum of the residue indicated the formation of the thioketone com-
plex 13, the S2O complex 10, and the S2O2 complex 20 in the molar
ratio of 50:43:7. The residue was subjected to column chromatogra-
phy (silica gel, CH2Cl2/Et2O, 5:1) to give a mixture of 14 and 13
(14 mg), and 10 (7.4 mg, 0.61 molar equiv.). The S2O2 complex 20
was not eluted from the silica-gel column. The molar ratio of 14
and 13 was 31:69, giving calculated yields of 0.0042 mmol (0.28
molar equiv.) and 0.010 mmol (0.66 molar equiv.), respectively.
When a solution of 16 (10 mg, 0.0065 mmol) in benzene (1.5 mL)
was heated at 50 °C, 1.0 mg of unidentifiable precipitates (ESI-MS:
m/2z ϭ 999.5) were collected by filtration.
[27]
[28]
[29]
[30]
[31]
[32]
[33]
[34]
Photolysis of 16: A solution of 16 in CDCl3 in an NMR tube was
irradiated with a high-pressure Hg lamp through a Pylex filter in
an ice-water bath for 1 h. The 31P NMR spectrum showed the for-
mation of the S2O2 complex 20, [(PPh3)2PtCl2], Ph3PϭO, and
Ph3PϭS in the molar ratio of 19:24:40:16. The signals due to the
S2O complex 10 were not observed (it was verified by a controlled
experiment that 10 barely decomposed under the conditions).
A. Ishii, M. Saitoh, M. Murata, J. Nakayama, Eur. J. Org.
Chem. 2002, 979Ϫ982.
W. Adam, J. Bialas, L. Hadjiarapoglou, Chem. Ber. 1991, 124,
2377.
W. Adam, L. Hadjiarapoglou, A. Smerz, Chem. Ber. 1991,
124, 227Ϫ232.
A. Shaver, M. El-khateeb, A.-M. Lebuis, Angew. Chem. 1996,
108, 2510Ϫ2512; Angew. Chem. Int. Ed. Engl. 1996, 35,
2362Ϫ2363.
Acknowledgments
We are grateful to Dr. Hideki Saito (Saitama University) for kind
discussion on the X-ray analysis of 10. This work was supported
by a Grant-in-Aid for Scientific Research (No. 12440174) from the
Ministry of Education, Culture, Sports, Science and Technology,
Japan.
[35]
Crystal data for 10: C36H30OP2PtS2·0.5C6H6 (C39H33OP2PtS2),
Mw ϭ 838.858, yellow plate, 0.30 ϫ 0.16 ϫ 0.06 mm3, mono-
clinic, space group P21/c, a ϭ 9.6861(6), b ϭ 21.5760(10), c ϭ
[1]
3
˚
˚
W. A. Schenk, Angew. Chem. 1987, 99, 101Ϫ112; Angew. Chem.
20.540(2) A, β ϭ 126.779(9)°, V ϭ 3438.1(4) A , Z ϭ 4,
Int. Ed. Engl. 1987, 26, 98Ϫ109.
ρ
calcd. ϭ 1.621 g cmϪ3, µ(Mo-Kα) ϭ 4.326 mmϪ1. Intensity data
[2]
K. K. Pandey, Prog. Inorg. Chem. 1992, 40, 445Ϫ502.
of 7920 independent reflections were collected in the range of
Ϫ12 Յ h Յ 12, 0 Յ k Յ 28, Ϫ26 Յ l Յ 12 with a Mac Science
MXC18 diffractometer using graphite-monochromated Mo-Kα
[3]
A. F. Hill, Adv. Organomet. Chem. 1994, 36, 159Ϫ227.
[4]
A. Müller, W. Jaegermann, J. H. Enemark, Coord. Chem. Rev.
˚
1982, 46, 245Ϫ280.
radiation (λ ϭ 0.71073 A) at 298 K. The structure was solved
[5]
J. E. Hoots, D. A. Lesch, T. B. Rauchfuss, Inorg. Chem. 1984,
by direct methods using SIR[42] and refined with full-matrix
23, 3130Ϫ3136.
least-squares (SHELXL-97[43]) using all the independent reflec-
3720
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2003, 3716Ϫ3721

Oxosulfido Complexes of Platinum
SHORT COMMUNICATION
tions for 442 parameters. Absorption corrections were done by
a psi-scan method. The non-hydrogen atoms were refined an-
isotropically, and hydrogen atoms were placed at calculated po-
sitions. Final R1 ϭ 0.0608 [I Ͼ 2σ(I), 6880 reflections], wR2 ϭ
R1 ϭ 0.0606 [I Ͼ 2σ(I), 4874 reflections], wR2 ϭ 0.1212 (for
all), GOF ϭ 0.888; max/min residual density ϭ 0.807/Ϫ0.708
Ϫ3
˚
e·A
.
CCDC-212018 (10) and CCDC-212019 (17) contain the sup-
plementary crystallographic data for this paper. These data can
be obtained free of charge via www.ccdc.cam.ac.uk/conts/re-
trieving.html (or from the Cambridge Crystallographic Data
Centre, 12, Union Road, Cambridge CB21EZ, UK; fax: (in-
ternat.) ϩ44-1223/336-033; or deposit@ccdc.cam.ac.uk).
A. Ishii, T. Kawai, J. Nakayama, unpublished results.
V. W. Day, D. A. Lesch, T. B. Rauchfuss, J. Am. Chem. Soc.
1982, 104, 1290Ϫ1295.
0.1465 (for all), GOF ϭ 1.315; max/min residual density ϭ
Ϫ3
˚
˚
1.584/Ϫ2.129 e·A . Selected bond lengths [A] and angles
[deg]: Pt(1A)ϪS(1A) 2.34(2), Pt(1A)ϪS(2A) 2.362(18),
Pt(1A)ϪP(1) 2.286(6), Pt(1A)ϪP(2) 2.267(6), S(1A)ϪO(1A)
1.50(3), S(1A)ϪS(2A) 2.09(3), S(1A)ϪPt(1A)ϪS(2A) 52.7(6),
P(1)ϪPt(1A)ϪS(1A) 102.0(5), P(2)ϪPt(1A)ϪS(2A) 102.5(5),
P(1)ϪPt(1A)ϪP(2) 102.0(2), P(2)ϪPt(1A)ϪS(1A) 153.4(5),
P(1)ϪPt(1A)ϪS(2A) 154.6(5), Pt(1B)ϪS(1B) 2.292(17),
Pt(1B)ϪS(2B) 2.30(3), Pt(1B)ϪP(1) 2.270(7), Pt(1B)ϪP(2)
2.320(6), S(1B)ϪO(1B) 1.456(17), S(1B)ϪS(2B) 2.09(3),
S(1B)ϪPt(1B)ϪS(2B) 54.1(7), P(1)ϪPt(1B)ϪS(1B) 155.2(4),
P(2)ϪPt(1B)ϪS(2B) 157.9(7), P(1)ϪPt(1B)ϪP(2) 100.9(3),
P(2)ϪPt(1B)ϪS(1B) 103.8(4), P(1)ϪPt(1B)ϪS(2B) 101.2(7).
Crystal data for 17: C47H44P2PtS3·2CHCl3 (C49H46Cl6P2PtS3),
Mw ϭ 1200.855, yellow plate, 0.18 ϫ 0.12 ϫ 0.06 mm3, mono-
[36]
[37]
We reported in a previous paper[31] that the dithiirane 19 de-
composes to thioketone 14 upon treatment with 4 in dichloro-
methane.
R. Ugo, G. L. Monica, S. Cenini, F. Conti, J. Chem. Soc., (A)
1971, 522Ϫ528.
R. Huang, I. A. Guzei, J. H. Espenson, Organometallics 1999,
18, 5420Ϫ5422.
I.-P. Lorenz, J. Kull, Angew. Chem. 1986, 98, 276Ϫ278; Angew.
Chem. Int. Ed. Engl. 1986, 25, 261Ϫ262.
A. Altomare, G. Cascarano, C. Giacovazzo, A. Guagliardi, J.
Appl. Crystallogr. 1993, 26, 343Ϫ350.
G. M. Sheldrick, SHELXL-97, Program for Crystal Structure
Refinement, Göttingen University, Germany, 1997.
R. H. Blessing, Acta Crystallogr., Sect. A 1995, 51, 33Ϫ38.
Received June 6, 2003
[38]
[39]
[40]
[41]
[42]
[43]
[44]
clinic, space group P21/n, a ϭ 15.0340(9), b ϭ 20.890(2), c ϭ
3
˚
˚
16.1150(10) A, β ϭ 98.270(3)°, V ϭ 5008.5(6) A , Z ϭ 4,
ρcalcd. ϭ 1.593 g cmϪ3, µ(Mo-Kα) ϭ 3.344 mmϪ1. 9865 inde-
pendent reflections were collected in the range of Ϫ19 Յ h Յ
16, 0 Յ k Յ 26, 0 Յ l Յ 20 with a Mac Science DIP3000
diffractometer using graphite-monochromated Mo-Kα radi-
˚
ation (λ ϭ 0.71073 A) at 298 K. Absorption corrections were
done by a multi-scan method (SORTAV[44]). 581 parameters,
Eur. J. Inorg. Chem. 2003, 3716Ϫ3721
www.eurjic.org
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3721