Reaction of 3,3-di-tert-butylthiirane-2-thione S-oxide (α-dithiolactone S-oxide): synthesis of thiolato sulfinato-platinum and palladium complexes

Article abstract of DOI:10.1016/j.tet.2007.04.004

Thermolysis of 3,3-di-tert-butylthiirane-2-thione S-oxide 4 gave di-tert-butyl ketone 5 and carbon disulfide (CS₂). Treatment of α-dithiolactone S-oxide 4 with excess m-CPBA or triphenylphosphine gave di-tert-butylthioketene S-oxide 3 almost quantitatively. Treatment of 4 with (η²-ethylene)bis(triphenylphosphine)platinum(0) 13 or tetrakis(triphenylphosphine) palladium 17 resulted in the formation of thiolato sulfinato-platinum complex 15 or palladium complex 18, respectively. The structure of complex 15 was determined by X-ray crystallographic analysis.

Full text of DOI:10.1016/j.tet.2007.04.004

Tetrahedron 63 (2007) 5161–5166
Reaction of 3,3-di-tert-butylthiirane-2-thione S-oxide
(a-dithiolactone S-oxide): synthesis of thiolato
sulfinato-platinum and palladium complexes
a
Toshiyuki Shigetomi, Kosei Shioji, Kentaro Okuma, Tohru Inoue and Yoshinobu Yokomori
a
a,*
a
b
a
Department of Chemistry, Faculty of Science, Fukuoka University, Jonan-ku, Fukuoka 814-0180, Japan
b
National Defense Academy, Hashirimizu, Yokosuka 239-8686, Japan
Received 8 March 2007; revised 2 April 2007; accepted 2 April 2007
Available online 6 April 2007
2
Abstract—Thermolysis of 3,3-di-tert-butylthiirane-2-thione S-oxide 4 gave di-tert-butyl ketone 5 and carbon disulfide (CS ). Treatment of
a-dithiolactone S-oxide 4 with excess m-CPBA or triphenylphosphine gave di-tert-butylthioketene S-oxide 3 almost quantitatively. Treatment
of 4 with (h -ethylene)bis(triphenylphosphine)platinum(0) 13 or tetrakis(triphenylphosphine) palladium 17 resulted in the formation of
2
thiolato sulfinato–platinum complex 15 or palladium complex 18, respectively. The structure of complex 15 was determined by X-ray crys-
tallographic analysis.
Ó 2007 Elsevier Ltd. All rights reserved.
1
. Introduction
2. Results and discussion
2.1. Thermolysis of 4
Sulfines (1) (thioketone S-oxide) belong to a class of
heterocumulenes, and are synthesized by oxidizing thioke-
1
1d,2
3
tone with peracid, ozone,
tions of sulfines 1 with thioketones, alkenes, acetylenes,
or singlet oxygen. The reac-
a-Dithiolactone S-oxide 4 was synthesized by reacting 2
with m-CPBA (1.2 equiv) (Scheme 1). Compound 4 left
4
5
6
12
7
8
9
dienes, nucleophiles, metal complexes, or thiation re-
agent are well known. Recently, we have reported the
in CDCl at room temperature for 1 day was recovered
3
1
0
unchanged. To confirm its thermal stability, 4 was refluxed
in CDCl , which resulted in the formation of di-tert-butyl
synthesis of 3,3-di-tert-butylthiirane-2-thione (2) from di-
tert-butylthioketene S-oxide (3) with Lawesson reagent
LR). Oxidation of 2 with m-chloroperoxybenzoic acid
m-CPBA) gave 3,3-di-tert-butylthiirane-2-thione S-oxide
4), another type of sulfine, the structure of which was
3
1
1
ketone (5) and carbon disulfide (CS ) in almost quantitative
2
yield. When refluxed in toluene-d , 4 was decomposed
8
1
2
(
(
(
within 30 min. Pushkara Rao and Ramamurthy described
that the thermolysis or photolysis of sulfines 1 gave the cor-
1
3
determined by X-ray crystallographic analysis (Chart
responding ketones and elemental sulfur. Although they
stated that the phototransformation might proceed through
oxathiirane intermediates, no explanation was given for
the thermolysis of 1, suggesting that the reaction mechanism
for the thermolysis of 1 is unclear. Thus, we attempted to
elucidate the reaction mechanism for the thermolysis of sul-
1
2a
1
). It is interesting to compare the reactivity of 4 with
that of normal sulfines. Herein, we describe the reaction of
and the isolation of platinum and palladium complexes
4
from 4.
1
fine 1. The rate of thermolysis of 4 was monitored by H
NMR spectroscopy, and a first-order reaction with a rate
ꢁ
2
ꢁ1
constant of 4.82ꢀ10 min at 353 K in toluene-d was
O
S
O
S
8
R
R
S
C S
O
observed. Variable temperature NMR spectroscopy over the
range of 333–363 K with toluene-d as solvent was used
to obtain activation parameters DH ¼82.6 kJ mol
S
S
8
z
ꢁ1
and
1
2
3
4
Chart 1.
m-CPBA
2
4
CH2Cl2
*
0
Corresponding author. Tel.: +81 92 871 6631; fax: +81 92 865 6030;
e-mail: kokuma@fukuoka-u.ac.jp
Scheme 1.
040–4020/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2007.04.004

5162
T. Shigetomi et al. / Tetrahedron 63 (2007) 5161–5166
z
ꢁ1
ꢁ1
DS ¼ꢁ71.6 J K mol . The rate of thermolysis of 4 in
COOMe
CD CN was lower than that in toluene-d . The above result
3
8
and the negative entropy of activation might be an indication
of the presence of a rigid cyclic intermediate 7 that was
responsible for the decomposition of 4. Presumably, the ini-
tially formed 7 via ionic intermediate 6 was further decom-
COOMe
8
9
COOMe
COOMe
posed to give di-tert-butyl ketone 5 and CS (Scheme 2).
2
S
S
S
S
O
S
S
10a
10b
Δ
O
4
S
Chart 2.
S
6
O
S
fluoride. Apparently, 4 is not reactive enough to intercept
DMAD 8 and benzyne 9.
O
+ CS2
S
7
5
8
4
5
CDCl3
Scheme 2.
O
S
COOMe
COOMe
2
.2. Reaction of 4
S
TMS
11
The oxidation of 4 with excess m-CPBA gave 3 almost quan-
titatively (Scheme 3). Presumably, SO or SO was further
2
12
OTf
extruded from the initially formed episulfide S-oxide or
S,S-dioxide to give 3. Schaumann and Behrens reported
that the oxidation of a-thiolactone afforded the correspond-
ing ketene, the intermediate of which might be episulfide
F
no reaction
4
+
9
CH2Cl2
1
4
S-oxide. The present result is similar to that of Schaumann
and Behrens. Desulfurization of 4 by triphenylphosphine in
refluxing CDCl gave 3 in almost quantitative yield along
Scheme 4.
3
with triphenylphosphine sulfide. The ring strain of the epi-
sulfide led to the elimination of the sulfur of 4. The reaction
of 4 with LR at room temperature afforded corresponding 2,
suggesting that the initially formed thiosulfine was further
isomerized to give dithiirane, the sulfur atom of which was
extruded to give 2.
2
.3. Synthesis of platinum and palladium complexes
Gosselink et al. have described the synthesis of sulfine–plat-
inum complexes. Several sulfur–platinum complexes
synthesized from (h -ethylene)bis(triphenylphosphine)pla-
tinum(0) (13) are also well known, including thioketone–
platinum complexes, dithiolato–platinum complexes,
9
a–c
2
1
5
1
5e
15e
On
15f
and thiolato sulfinato–platinum complexes. We have al-
ready reported that the reaction of 2 with 13 afforded dithio-
S
excess m-CPBA
O
3
1
2b
4
lato–platinum complex (14). Thus, we tried to synthesize
the platinum complex by reacting 4 with 13. Treatment of 4
with 13 at room temperature resulted in the formation of
thiolato sulfinato–platinum complex (15) in 91% yield.
Weigand and Wusch assumed that the addition of soft
platinum(0) atom takes place probably at the soft thiolate
CH2Cl2
S
n=1 or 2
Ph3P
4
3
+
Ph3P=S
CDCl3
S
S
15a
LR
S
S
sulfur atom rather than at the hard sulfenate sulfur. Based
4
2
CDCl3
on the report by Weigand and Wusch, we propose the mech-
anism that the platinum atom in 13 attacks the episulfide
sulfur atom in 4 to give complex 15 (Scheme 5).
S
S
Scheme 3.
We have previously described that the reactions of 2 with di-
methyl acetylenedicarboxylate (DMAD) (8) or benzyne (9)
afforded 1,3-dithioles (10a) or (10b) in good yields, respec-
S
1
3
Pt(PPh3)2
4
CH2Cl2
O
1
2
tively (Chart 2). To compare the reactivity of 2 with that of
, we reacted 4 with DMAD 8 (Scheme 4). When 4 and 8 in
CDCl were refluxed for 1 day, di-tert-butyl ketone 5 was
S
4
O
S
3
PPh3
PPh3
1
obtained, and no cycloadduct (11) was detected by H
Pt
NMR spectroscopy of the crude mixture. Similarly, cycload-
dition did not take place on treatment of 4 with benzyne 9,
which was generated by reacting o-trimethylsilylphenyl tri-
fluoromethanesulfonate (12) with tetrabutylammonium
S
1
5
Scheme 5.

T. Shigetomi et al. / Tetrahedron 63 (2007) 5161–5166
5163
Figure 1. ORTEP drawing of complex 15.
Since the recrystallization of complex 15 from chloroform
gave single crystals, X-ray crystallographic analysis was
carried out. In the ORTEP drawing of 15 shown in Figure 1,
the crystal contained three molecules of chloroform per
two molecules of 15. Complex 15 has two molecular struc-
tures (15A and 15B). The bond lengths of the four-mem-
bered ring of 15A are similar to those of 15B. The bond
lengths of Pt–P and C]C of 15A are also similar to those
of 15B. However, the bond length of S]O of 15A is
shorter than that of 15B. The bond angles of the four-mem-
bered ring of 15A are similar to those of 15B. Comparison
with the X-ray crystallographic data of thiolato sulfinato–
platinum complex (16) (bond lengths: C–S: 1.871 and
P2A: 102.70(15), S1A–Pt1A–P1A: 90.21(15), S2A–Pt1A–
P2A: 93.16(16), C1A–S1A–Pt1A: 92.0(6), C1A–S2A–
Pt1A: 92.4(7), S2A–C1A–S1A: 101.2(9), O1A–S1A–C1A:
107.8(11), O1A–S1A–Pt1A: 111.8(8), S2B–Pt1B–S1B:
73.42(16), P1B–Pt1B–P2B: 105.51(16), S1B–Pt1B–
P2B: 90.65(16), S2B–Pt1B–P1B: 90.42(16), C1B–S1B–
Pt1B: 91.3(6), C1B–S2B–Pt1B: 93.8(7), S2B–C1B–S1B:
101.0(9), O1B–S1B–C1B: 106.3(9), O1B–S1B–Pt1B:
ꢂ
109.0(5) .
3
1
The P NMR spectrum of 15 showed two signals that
resonated at d 16.6 (JPt–P¼2390 Hz, J ¼26 Hz) and
P–P
17.6 (JPt–P¼3278 Hz, J ¼26 Hz). The chemical shifts
P–P
˚
1
angles: S–Pt–S: 70.4, C–S–Pt: 89.6, C–S–Pt: 92.0, and
.827, S–O: 1.473, Pt–S: 2.353, and Pt–S: 2.314 A. Bond
and the JPt–P values of the signals of 15 are similar to those
of the reported thiolato sulfinato–platinum complexes.
1
5f,h
1
5f
195
S–C–S: 93.4) demonstrated that the C–S bond lengths
of the four-membered ring of 15 are shorter than those
of 16 (Chart 3). The S–C–S bond angles of 15 are larger
than those of 16. In 15, the sum of the bond angles of
In the
Pt NMR spectrum, the signal representative of
values
of 15 are 2367 and 3303 Hz, which are the same as
15 was observed at d ꢁ4307 (Chart 4). The J
Pt–P
3
1
the data obtained by P NMR measurement. The values
of the platinum signal of 15 indicate that 15 is a Pt(II)
complex. Complex 14 showed a signal that resonated at
S2–Pt1–S1, P1–Pt1–P2, S1–Pt1–P1, and S2–Pt1–P2 is ca.
ꢂ
3
C1–S1–Pt1–S2 is also ca. 360 , suggesting that 15 is
60 , and the sum of the interior angles of the quadrangle
ꢂ
195
d ꢁ4399 (J ¼2948 Hz) in the
Pt–P
Pt NMR spectrum,
value of that signal
are similar to those of general dithiolato–platinum com-
planar.
and the chemical shift and the J
Pt–P
1
6
Selected bond lengths: C1A–C2A: 1.360(3), Pt1A–S2A:
plexes. The values of the signal of 15 are similar to those
of 14.
2
.303(4), Pt1A–S1A: 2.312(4), S1A–O1A: 1.457(19),
S1A–C1A: 1.800(2), S2A–C1A: 1.790(2), Pt1A–P1A:
.325(4), Pt1A–P2A: 2.336(4), C1B–C2B: 1.340(2),
Pt1B–S2B: 2.273(4), Pt1B–S1B: 2.331(4), S1B–O1B:
.530(14), S1B–C1B: 1.790(2), S2B–C1B: 1.773(18),
2
Gosselink et al. reported that the reactions of sulfines 1
with tetrakis(triphenylphosphine) palladium (17) gave
9
d
1
sulfine–palladium complex. To compare the reactivity
of palladium with that of platinum, we reacted 4 with 17.
The reaction gave thiolato sulfinatoꢁpalladium complex
˚
Pt1B–P2B: 2.333(4), Pt1B–P1B: 2.334(4) A. Selected
bond angles: S2A–Pt1A–S1A: 73.97(16), P1A–Pt1A–
3
1
(
18) in 85% yield (Scheme 6). In the P NMR spectrum,
complex 18 demonstrated signals that resonated at
d¼22.4 (J ¼64.5 Hz) and 25.8 (J ¼64.5 Hz). A band
P–P
P–P
O
assignable to the S]O bond in 18 was also observed at
1093 cm in the IR spectrum. To confirm the difference
ꢁ1
S
S
PPh3
PPh3
S
PPh3
PPh3
Pt(PPh3)2(η=C2H4)
Pt
Pt
in stability between 15 and 18, these two compounds
ꢂ
S
were left in dichloromethane at ꢁ20 C. After 1 day, 15
was recovered unchanged, whereas 18 was decomposed,
suggesting that 15 was more stable than 18 in the
solvent.
13
14
16
Chart 3.

5164
T. Shigetomi et al. / Tetrahedron 63 (2007) 5161–5166
195
Chart 4. Pt NMR spectrum of 15.
O
S
4. Experimental
Pd(PPh3)4
17
PPh3
Pd
4
4.1. General
CH2Cl2
S
PPh3
All chemicals were obtained from commercial suppliers and
were used without further purification. Analytical TLC was
carried out on precoated plates (Merck silica gel 60, F254)
and flash column chromatography was performed with silica
18
Scheme 6.
1
13
(Merck, 70–230 mesh). NMR spectra ( H at 400 MHz;
at 100 MHz; P at 162 MHz; and Pt at 86 MHz) were re-
C
3
1
195
3. Conclusion
corded in CDCl , and chemical shifts are expressed in parts
3
1
13
Thermolysis of a-dithiolactone S-oxide 4 gave di-tert-butyl
ketone 5 and CS . Moreover, variable temperature NMR
spectroscopy over the range of 333–363 K in toluene-d
per million relative to internal TMS for H and C, and ex-
ternal Na PtCl (D O) for Pt NMR. Melting points were
uncorrected.
1
95
2
2
6
2
8
z
ꢁ1
resulted in activation parameters DH ¼82.6 kJ mol and
z
ꢁ1
ꢁ1
DS ¼ꢁ71.6 J K mol . The reaction of 4 with excess
m-CPBA or triphenylphosphine gave di-tert-butylthioke-
tene S-oxide 3 almost quantitatively. The reaction of 4
with LR at room temperature afforded the corresponding
4.1.1. Thermolysis of 4. Compound 4 (0.011 g, 0.05 mmol)
was heated for 1 day in chloroform-d at 60 C. Decomposi-
ꢂ
tion of 4 and formation of di-tert-butyl ketone 5 and CS was
2
observed by NMR spectroscopy. The reaction mixture was
evaporated to give a colorless oil, which was chromato-
graphed over silica gel by elution with hexane–dichloro-
methane (1:1) to give pure 5 (0.0057 g, 0.04 mmol).
2
a-dithiolactone 2. Treatment of 4 with (h -ethylene)-
bis(triphenylphosphine)platinum(0) 13 or tetrakis(triphe-
nylphosphine) palladium 17 resulted in the formation of
thiolato sulfinato–platinum complex 15 or palladium
complex 18 in good yields, respectively. The structure of
complex 15 was determined by X-ray crystallographic
analysis.
4.1.2. Oxidation of 4. To a solution of 4 (0.011 g,
0.05 mmol) in dichloromethane (2 mL) was added a solution
of m-chloroperbenzoic acid (0.043 g, 0.25 mmol) in one por-
tion. After being stirred for 1 h, 10 mL of hexane was added
to the reaction mixture, which was filtered and evaporated to
give a deep-yellow solid, which was chromatographed over
silica gel by elution with hexane–dichloromethane (1:1) to
give pure 3 (0.009 g, 0.048 mmol).
CCDC 642214 contains the supplementary crystallographic
data for complex 15. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre
via www.ccdc.cam.ac.uk/data_request/cif.

T. Shigetomi et al. / Tetrahedron 63 (2007) 5161–5166
5165
4.1.3. Reaction of 4 with triphenylphosphine. Triphenyl-
phosphine (0.053 g, 0.20 mmol) was added to a solution of
Complex 15; formula C H OP PtS , FW 938.055, mono-
46 48 2 2
clinic, space group¼P2 , a¼12.7160(3), b¼15.4370 (4),
1
˚
ꢂ
m(Mo
4
(0.022 g, 0.10 mmol) in CDCl . A solution was heated
3
c¼24.6670 (6) A, a¼90.00, b¼93.9130(10), g¼90.00 ,
ꢂ
˚
3
ꢁ3
for 2 h in 60 C. The formation of 3 was monitored by
NMR spectroscopy. The reaction mixture was evaporated
to give a colorless solid, which was chromatographed over
silica gel by elution with hexane–dichloromethane (1:1) to
give pure 3 (0.018 g, 0.0968 mmol).
V¼4830.8(2) A ,
Z¼4,
D ¼1.290 Mg m
,
x
ꢁ
1
Ka)¼8.636 mm , the final R and wR were 0.0851 and
0.2200, respectively, using 16,533 reflections.
4.1.9. Synthesis of palladium complex 18. Tetrakis(tri-
phenylphosphine) palladium 17 (0.058 g, 0.05 mmol) was
added to a solution of 4 (0.011 g, 0.05 mmol) in dichlorome-
thane (2 mL). After the reaction mixture had been stirred for
30 min, it was evaporated to give black-yellow solid. The
residue was recrystallized from hexane–dichloromethane
(1:1) to give yellow crystals 18 (0.0361 g, 0.0425 mmol).
4
.1.4. Thiation of 4. Lawesson reagent (0.61 g, 0.15 mmol)
was added in one portion to a solution of 3,3-di-tert-butyl-
thiirane-2-thione S-oxide 4 (0.022 g, 0.10 mmol) in chloro-
form (4 mL). After being stirred for 3 h, the reaction
mixture was evaporated to give yellow oily crystals, which
were chromatographed over silica gel by elution with hexane
to give pure 2 (0.0186 g, 0.092 mmol).
ꢂ
Compound 18; yellow crystals; mp 125.1–128.8 C (dec);
1
H NMR (CDCl , 400 MHz) d¼1.35 (s, 9H), 1.43 (s, 9H),
3
1
3
7
.14–7.42 (m, 30H);
C NMR (CDCl , 100 MHz)
3
4
8
.1.5. Reaction of 4 with dimethyl acetylenedicarboxylate
. To a solution of 4 (0.026 g, 0.12 mmol) in CDCl3
d¼31.66, 33.08, 40.26, 42.45, 128.06, 128.16, 128.27,
128.37, 130.07, 130.84, 130.90, 131.18, 131.27, 134.36,
134.46, 134.48, 134.58, 145.49, 150.17; P NMR (CDCl3,
3
1
was added dimethyl acetylenedicarboxylate 8 (0.018 g,
ꢂ
0
.20 mmol). The solution was heated for 1 day in 60 C and
162 MHz) d¼22.4 (J ¼64.5 Hz), 25.8 (J ¼64.5 Hz);
P–P
P–P
1
ꢁ1
the reaction was monitored by H NMR spectroscopy. The
reaction mixture was evaporated to give a colorless oil,
which was chromatographed over silica gel by elution with
hexane–dichloromethane (1:1) to give pure 5 (0.0142 g,
IR n¼1093 cm (S]O); Anal. Calcd for C H OP S Pd:
4
6
48
2 2
C, 65.05; H, 5.70. Found: C, 65.44; H, 5.94.
Supplementary data
0
.10 mmol).
Supplementary data associated with this article can be found
in the online version, at doi:10.1016/j.tet.2007.04.004.
4
.1.6. Reaction of 4 with benzyne 9. Tetrabutylammonium
fluoride in THF complex (1.0 M) (0.12 mL, 0.12 mmol) was
added to a solution of 4 (0.022 g, 0.1 mmol) and o-trimethyl-
silylphenyl trifluoromethanesulfonate (0.030 g, 0.1 mmol)
in dichloromethane (5 mL). After the reaction mixture had
been stirred for 0.5 h, it was evaporated to give a red-yellow
oil, which was washed with water and extracted with hexane.
The combined extracts were dried over magnesium sulfate,
filtered, and evaporated to give orange oily crystals, which
were chromatographed over silica gel by elution with hex-
ane–dichloromethane (1:1) to recover 4.
References and notes
1. (a) Battaglia, A.; Dondoni, A.; Giorgianni, P.; Maccagnani, G.;
Mazzanti, G. J. Chem. Soc. B 1971, 1547; (b) Zwanenburg, B.;
Thijs, L.; Strating, J. Recl. Trav. Chim. Pays-Bas 1967, 86, 577;
(c) Hasserodt, J.; Pritzkow, H.; Sundermeyr, W. Chem. Ber.
1993, 127, 1701; (d) Zwanenburg, B.; Janssen, W. A. J.
Synthesis 1973, 617; (e) Carlsen, L.; Snyder, J. P.; Holm, A.;
Pederson, E. Tetrahedron 1981, 37, 1257; (f) Adiwidjaja, G.;
Sawluk, A.; Volz, W.; Voss, J. Phosphorus, Sulfur Silicon
Relat. Elem. 1973, 74, 451; (g) Cerreta, F. Bull. Soc. Chim.
Fr. 1995, 67, 132.
2. Tabuchi, T.; Nojima, M.; Kusabayashi, S. J. Chem. Soc., Perkin
Trans. 1 1991, 3043.
3. Ramnath, N.; Ramesh, V.; Ramamurthy, V. J. Org. Chem. 1983,
48, 214.
4. (a) Huisgen, R.; Mloston, G.; Polborn, K.; Sustmann, R.;
Sicking, W. Liebigs Ann. Recl. 1997, 179; (b) Huisgen, R.;
Mloston, G.; Polborn, K. J. Org. Chem. 1996, 61, 6570.
5. (a) Adam, W.; Deeg, O.; Weink €o tz, S. J. Org. Chem. 1997,
62, 7084; (b) Adam, W.; Weink €o tz, S. J. Am. Chem. Soc.
1998, 130, 4861.
2
4
(
.1.7. Synthesis of platinum complex 15. (h Ethylene)bis-
triphenylphosphine)-platinum(0) 13 (0.037 g, 0.05 mmol)
was added to a solution of 4 (0.011 g, 0.05 mmol) in di-
chloromethane (2 mL). After the reaction mixture had been
stirred for 10 min, it was evaporated to give black-yellow
solid. The residue was recrystallized from chloroform to give
yellow crystals 15 (0.0427 g, 0.0455 mmol). Compound 15;
ꢂ
1
yellow crystals; mp 223.3–227.0 C (dec); H NMR (CDCl ,
3
4
00 MHz) d¼1.36 (s, 9H), 1.40 (s, 9H), 7.16–7.46 (m, 30H);
1
3
C NMR (CDCl , 100 MHz) d¼32.17, 33.27, 39.93, 42.29,
3
128.17, 128.27, 128.35, 128.45, 129.99, 130.46, 130.69,
130.75, 134.81, 134.84, 134.93, 134.96; P NMR (CDCl3,
1
3
1
62 MHz) d¼16.6 (J ¼2390 Hz, J ¼26 Hz), 17.6
Pt–P
P–P
1
95
(
J
¼3278 Hz,
J
¼26 Hz);
Pt–P
Pt NMR (CDCl ,
3
6. Adam, W.; Fr €o hling, B.; Weink €o tz, S. J. Org. Chem. 1998, 63,
9154.
7. Zwanenburg, B.; Thijs, L.; Broens, J. B.; Strating, J. Recl. Trav.
Chim. Pays-Bas 1972, 91, 443.
Pt–P
P–P
8
6 MHz, Na PtCl ) d¼ꢁ4307 (J ¼2367, 3303 Hz); IR
ꢁ
46 48 2 2 2
2
6
1
n¼1093 cm (S]O); Anal calcd for C H P S Pt$H O:
C, 59.92; H, 5.25. Found: C, 59.82; H, 5.33.
.1.8. X-ray crystallographic analysis of complex 15. Sin-
gle crystals of 15 were obtained by recrystallization from
8
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4
chloroform. The diffraction data were collected with a DIP
Image Plate diffractometer with Cu Ka radiation
ꢂ
The structure was solved by SIR92 and refined SHELXL-97.
(
l¼1.54184) to a maximum 2q value of 140.16 at 293 K.

5
166
T. Shigetomi et al. / Tetrahedron 63 (2007) 5161–5166
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1
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