Isolation and reaction of 1,2-dithietan-3-one: Formation of thiolato thiocarboxylato metal complexes

Article abstract of DOI:10.1246/bcsj.82.855

The reaction of 4,4-di-tert-butyl-1,2-dithietan-3-one with triphenylphosphine afforded 1,1-di-tert-butylthiiran-2-one (86%). The reaction of 4,4-di-tert-butyl-1,2-dithietan-3-one with phenylmagnesium bromide gave S-phenyl 2-tertbutyl-2-mercapto-3,3-dimeth

Full text of DOI:10.1246/bcsj.82.855

© 2009 The Chemical Society of Japan
Bull. Chem. Soc. Jpn. Vol. 82, No. 7, 855–859 (2009)
855
Isolation and Reaction of 1,2-Dithietan-3-one: Formation of
Thiolato Thiocarboxylato Metal Complexes
Toshiyuki Shigetomi,1 Kentaro Okuma,*1 Noriyoshi Nagahora,1 and Yoshinobu Yokomori2
1Department of Chemistry, Faculty of Science, Fukuoka University, Jonan-ku, Fukuoka 814-0180
2National Defense Academy, Hashirimizu, Yokosuka 239-8686
Received January 8, 2009; E-mail: kokuma@fukuoka-u.ac.jp
The reaction of 4,4-di-tert-butyl-1,2-dithietan-3-one with triphenylphosphine afforded 1,1-di-tert-butylthiiran-2-
one (86%). The reaction of 4,4-di-tert-butyl-1,2-dithietan-3-one with phenylmagnesium bromide gave S-phenyl 2-tert-
butyl-2-mercapto-3,3-dimethylbutanethioate in 83% yield. The reaction of 4,4-di-tert-butyl-1,2-dithietan-3-one with
tetrakis(triphenylphosphine)palladium(0) gave square-planar complex in 84% yield, whose structure was determined by
X-ray crystallographic analysis.
Three- and four-membered cyclic compounds containing
two heteroatoms have been studied extensively.1 Because of
their unique structures and chemical reactivities, three- and
four-membered rings containing an S-S bond have also
received great attention from both experimental and theoretical
perspectives.2 1,2-Dithietanes 1, in particular, have stimulated
fundamental theoretical and chemical interests.1 Isolated
examples of compounds bearing the 1,2-dithietane ring system
are dithiatopazine 1a, 3,4-diethyl-1,2-dithietane 1,1-dioxide
1b, and sulfurane 1c.3-5 On the other hand, five-membered ring
compounds containing an S-S bond, such as 1,2-dithiolan-3-
ones and 1,2-dithiolan-3-one 1-oxides6,7 are well known, which
are of interest because of their chemical behavior and bio-
logical activities. We have also reported the synthesis of five-
membered disulfide, 1,2-dithiolan-3-thione, which reacted with
benzyne to afford spirocyclic 1,3-benzodithiol.8 In a previous
paper, we have communicated the isolation of 1,2-dithietan-
3-ones 2, which are four-membered analogs of 1a and 1b.
(Chart 1).9 In this paper, we would like to show full details of
the isolation and reaction of 2.
di-tert-butyl thioketene with nitrones such as 5,5-dimethyl-1-
pyrroline N-oxide.11 However, the scope and limitation were
not described. Nicolaou et al. reported that the reaction of
dithiatopazine 1a with triphenylphosphine gave an episulfide
and triphenylphosphine sulfide.4 Thus, we attempted the
synthesis of ¡-thiolactone 4a from 1,2-dithietan-3-one 2a and
triphenylphosphine. One sulfur atom in 2a was eliminated by
treatment with triphenylphosphine in CDCl3 at room temper-
ature for 4 days to give 3,3-di-tert-butylthiiran-2-one (4a) in
82% yield along with triphenylphosphine sulfide (Scheme 2).
Thus, a completely different method for the synthesis of ¡-
thiolactone was achieved.
Thermal Behavior of 1,2-Dithietan-3-one. Nicolaou et al.
reported that dithiatopazine 1a was thermally decomposed
when heated in xylene at 140 °C for 1 h to give an olefinic
compound and diatomic sulfur.4 To compare the stability of
O
N
O
C C
S
S
S
O
OEt
S
O
S
Results and Discussion
3a
2a
As shown in a preliminary communication,10 1,2-dithietan-
3-one 2a was synthesized by cycloaddition and cycloreversion
of 3,3-di-tert-butylthiiran-2-thione (3a) with nitrile oxide
generated from ethyl chlorooxyimidoacetate and triethylamine
in 82% yield (Scheme 1). 5,5,9,9-Tetramethyl-1,2-dithiaspiro-
[3,5]non-3-one (2b) was also synthesized in 80% yield.
Synthesis of ¡-Thiolactone 5. According to Schaumann
and Behrens, ¡-thiolactones 4 were synthesized by oxidation of
O
S
N
C C
S
OEt
O
S
3b
2b
Scheme 1.
F3C
CF3
O
S
O
S
Ph3P
O
S
O
+ Ph3P=S
2a
H
Ph
H
S
S
S
O
S
O
S
O
Et
Et
R
O
S
R
O
Ph
4a
Scheme 2.
1a
1b
1c
2
Chart 1.
Published on the web July 10, 2009; doi:10.1246/bcsj.82.855

856
Bull. Chem. Soc. Jpn. Vol. 82, No. 7 (2009)
Isolation and Reaction of 1,2-Dithietan-3-one
reflux, 48 h
no reaction
2a
Xylene
Scheme 3.
S
R'
S
R
R
Path A
Path B
R'
MgBr
Path A
S
5
O
Path B
S
S
R
R
R'
Figure 1. ORTEP drawing of compound 6a. Selected bond
lengths [¡] and angles [°] of 6a. S1-C11 1.776(2), S1-C1
1.8003(17), S2-C2 1.8506(17), O1-C1 1.200(2), C1-C2
1.549(2); C11-S1-C1 98.90(8), O1-C1-C2 122.46(15),
O1-C1-S1 120.63(13), C2-C1-S1 116.91(11), C1-C2-S2
109.03(11).
Path C
S
R
6
O
O
S
R
2
S
Path C
R'
R
R
O
S
H
7
RMgBr
THF
2a
Scheme 4.
SR
O
dithiatopazine with that of 2a, 2a was refluxed in xylene-d10 at
140 °C for 2 days. Surprisingly, 2a was recovered unchanged,
suggesting that 2a was more stable than 1a (Scheme 3). Since
sublimation of 2a was observed at 160 °C, the thermal stability
of dithiatopazine and 2a was quite different.
6a: R = Ph 83%
6b: R = Me 78%
6c: R = n-Pr 77%
Scheme 5.
Reaction of 1,2-Dithietan-3-one
2
with Grignard
Reagents. Unusual thermal stability of 2 prompted us to
investigate reactivity of 2a toward a nucleophile. To confirm
the reactivity of 2 toward nucleophiles, the reaction of 2a
with Grignard reagents was carried out. Three pathways are
plausible in the reaction of 1,2-dithietan-3-one 2 with Grignard
reagents (Scheme 4).
When 2a was reacted with phenylmagnesium bromide, only
1
one isomer was obtained. In the H NMR spectrum, signals of
methyl and aromatic protons resonated at ¤ 1.32 (18H) and 7.43
(5H), respectively. In the 13C NMR spectrum, signals of C=O
and quaternary ring carbon resonated at ¤ 203.27 and 80.53,
respectively. In the IR spectrum, a band assignable to C=O was
observed at 1677 cm¹1. The above results indicate that the
product is not isomer 7 but isomers 5 or 6. Finally, the structure
of the product was determined by X-ray crystallographic
analysis (Figure 1). The obtained product was S-phenyl 2-tert-
butyl-2-mercapto-3,3-dimethylbutanethioate (6a). S-Methyl 2-
tert-butyl-2-mercapto-3,3-dimethylbutanethioate (6b) and S-
propyl 2-tert-butyl-2-mercapto-3,3-dimethylbutanethioate (6c)
were also synthesized in a similar manner (Scheme 5). In
addition, the reaction of 2a with methyllithium also afforded
butanethioate 6b in 77% yield.
In order to elucidate the electronic structure and reactivity of
compound 2, we carried out theoretical calculations for 4,4-di-
tert-butyl-1,2-dithietan-3-one (2a). In the structural optimiza-
tion of the model molecule using the B3LYP method,12 one
local minimum of 2a was found with geometries similar to the
crystalline structure of 2b. The composition of the LUMO
orbitals of 2a is depicted in Figure 2. It was found that the
LUMO is located on ·*-orbitals of the sulfur-sulfur bond of
Figure 2. Plot of the LUMO orbitals of 2a at the B3LYP/
6-311+G(d,p) level.
2a, indicating the disulfide moiety of 2a is very highly reactive
toward nucleophiles. Mulliken atomic charges of 2a showed
the sulfur atom at the 2-position is more positive than the 1-
position (Table 1). Additionally, the sulfur atom at the 2-
position is less bulky than that at the 3-position.
To compare thermal stability of 5 and 6, total energies
(corrected with zero-point energies) of 2-methyl-2-(methyl-
thio)propanethioic acid (5d) and S-methyl 2-mercapto-2-meth-
ylpropanethioate (6d) were calculated at the B3LYP/6-31G(d)
level (Chart 2).12 The result showed that 6d was found to be
8.90 kJ mol¹1 more stable than 5d at the ground-state S0. Thus,
the regioselective formation of compounds 6a-6c in the
reactions of 2a with Grignard reagents can be supported by
the theoretical calculations of 2a together with a consideration
for bulkiness of the tert-butyl groups of 2a (Scheme 6).

T. Shigetomi et al.
Bull. Chem. Soc. Jpn. Vol. 82, No. 7 (2009)
857
Table 1. Mulliken Atomic Charges of 2a
S2 S1
t-Bu
O
t-Bu
Basis set
S1
S2
6-31G(d)
6-311+G(d,p)
¹0.015
¹0.654
+0.082
+0.037
H3C
H3C
SH
O
H3C
H3C
SCH3
SH
SCH3
Figure 3. ORTEP drawing of complex 9. Selected bond
lengths [¡] and angles [°] of 9. Pt1-P2 2.2870(9), Pt1-S2
2.3028(9), Pt1-S1 2.3058(9), Pt1-P1 2.3110(9), S1-C1
1.764(4), S2-C2 1.852(4), O1-C1 1.212(4), C1-C2
1.535(5); P2-Pt1-S2 88.31(3), S2-Pt1-S1 85.95(3),
P2-Pt1-P1 97.08(3), S1-Pt1-P1, 89.23(3), C1-S1-Pt1
108.43(12), C2-S2-Pt1 109.52(12), O1-C1-C2 122.5(3),
O1-C1-S1 116.3(3), C2-C1-S1 121.2(2), C1-C2-S2
111.0(2).
O
5d
6d
Chart 2.
SH
SR'
O
H+
Path B
S
S
R'
O
Pd(PPh3)4
S
2a
6
PPh3
10
2a
Pd
Scheme 6.
CH2Cl2
PPh3
S
O
11
Pt(PPh3)2(η2C2H4)
S
PPh3
PPh3
Scheme 8.
8
2a
Pt
195Pt NMR signals of dithiolato-platinum complexes and their
analogs were observed in the range of ¤ ¹4400- ¹5060.15 The
chemical shifts of the above complexes are similar to that of
9, indicating that 9 is a PtII complex. X-ray crystallographic
analysis of 9 was carried out. In the ORTEP drawing of 9
shown in Figure 3, the crystal contained one molecule of
acetonitrile (recrystallization solvent) per one molecule of 9.
The sum of bond angles of P2-Pt1-S2, S2-Pt1-S1, P2-Pt1-P1,
and S1-Pt1-P1 is ca. 360°, suggesting that complex 9 has
planar structure (also see Supporting Information; Table S14).
To compare the reactivity of palladium with that of platinum
toward 1,2-dithietan-3-one 2a, the reaction of 2a with
tetrakis(triphenylphosphine)palladium(0) (10) was carried out.
Treatment of 2a with 10 at room temperature resulted in the
formation of thiolato thiocarboxylato-palladium complex 11 in
84% yield (Scheme 8).
CH2Cl2
S
O
9
Scheme 7.
Synthesis of Platinum and Palladium Complexes from
1,2-Dithietan-3-one. In recent years, several sulfur-platinum
complexes have been synthesized.13 Previously, we have
reported the reaction of ¡-dithiolactone 3a with (©2-ethyl-
ene)bis(triphenylphosphine)platinum(0) (8) afforded the corre-
sponding dithiolato-platinum complex.14 Although isolated
examples of dithiooxalato-platinum complexes and their
analogs are well known,15 to the best of our knowledge, there
are no reports on the isolation of thiolato thiocarboxylato-
platinum complex. Thus, we attempted the synthesis of thiolato
thiocarboxylato-platinum complex by reacting 1,2-dithietan-3-
one 2a with 8. Treatment of 2a with 8 at room temperature
resulted in the formation of thiolato thiocarboxylato-platinum
complex 9 in 94% yield (Scheme 7).
Signals of methyl and aromatic protons appeared at ¤ 1.15
(s, 18H), 7.10-7.52 (m, 30H) in the 1H NMR spectrum.
In the 13C NMR spectrum, signals of C=O and quaternary
ring carbon of 9 resonated at ¤ 221.9 (JC-P = 20.7 Hz) and 71.4
(JC-P = 4.2 Hz), respectively. The 31P NMR spectrum of 9
showed two signals that resonated at ¤ 19.3 (JPt-P = 2846 Hz,
Signals of methyl and aromatic protons appeared at ¤ 1.15
1
(s, 18H), and 7.12-7.47 (m, 30H) in the H NMR spectrum. In
the 13C NMR spectrum, signals of C=O and the quaternary ring
carbon of 11 resonated at ¤ 220.27 (JC-P = 25.1 Hz) and 75.8
(JC-P = 6.7 Hz), respectively. The H and 13C NMR data of 11
1
are similar to those of platinum complex 9. The 31P NMR
spectrum of 11 showed two signals that resonated at ¤ 24.5
(JP-P = 52 Hz) and 32.6 (JP-P = 52 Hz). Finally, the structure of
11 was determined by X-ray crystallographic analysis. In the
ORTEP drawing of 11 shown in Figure 4, the crystal contained
one molecule of acetonitrile (recrystallization solvent) per one
molecule of 11. The sum of bond angles of S2-Pd1-P2, S1-
J
P-P = 27 Hz) and 26.0 (JPt-P = 3013 Hz, JP-P = 27 Hz). In
the 195Pt NMR spectrum, the signal representative of 9 was
observed at ¤ ¹4745 (JPt-P = 2846 and 3013 Hz). Generally,

858
Bull. Chem. Soc. Jpn. Vol. 82, No. 7 (2009)
Isolation and Reaction of 1,2-Dithietan-3-one
1
yellow crystals: mp 100-105 °C; H NMR (CDCl3, 400 MHz): ¤
1.10 (s, 6H), 1.31 (s, 6H), 1.47-1.61 (m, 4H), 1.73-1.79 (m, 2H).
13C NMR (CDCl3, 100 MHz): ¤ 18.20, 26.10, 29.25, 37.86, 38.90,
114.14, 193.94. IR ¯ = 1724 cm¹1 (C=O). UV-vis (hexane): -max
(¾) 292.5 (711), 398.0 (106). Anal. Calcd for C11H18OS2: C, 57.35;
H, 7.87%. Found: C, 57.04; H, 7.80%. HRMS Calcd for
C11H18OS2 (M+), 230.0799; Found 230.0822.
Reaction of 2a with Phenylmagnesium Bromide.
To a
solution of 2a (0.055 g, 0.25 mmol) in benzene was added
phenylmagnesium bromide in THF complex (1.0 M) (0.29 mL,
0.29 mmol) and stirred for 1 h. After being washed with water, the
reaction mixture was evaporated to give a pale yellow oil, which
was chromatographed over silica gel by elution with hexane to
give pure 6a (0.061 g, 0.20 mmol). 6a; colorless crystals; mp 52-
1
Figure 4. ORTEP drawing of complex 11. Selected bond
lengths [¡] and angles [°] of 11. Pd1-S1 2.2888(11), Pd1-
S2 2.2970(11), Pd1-P1 2.3170(10), Pd1-P2 2.3547(11),
S1-C2 1.858(4), S2-C1 1.766(4), C1-O1 1.212(5), C1-C2
1.531(6); S1-Pd1-S2 85.43(4), S1-Pd1-P1 87.88(4),
S2-Pd1-P2 89.79(4), P1-Pd1-P2 97.56(4), C2-S1-Pd1
110.29(14), C1-S2-Pd1 109.00(15), O1-C1-C2 122.5(4),
O1-C1-S2 116.6(4), C2-C1-S2 121.0(3), C1-C2-S1
110.2(3). R = 0.0497, wR = 0.1465.
58 °C; H NMR (CDCl3, 400 MHz): ¤ 1.32 (s, 18H), 2.34 (s, 1H),
7.35-7.43 (m, 5H); 13C NMR (CDCl3, 100 MHz): ¤ 30.91, 42.38,
¹1
80.53, 129.40, 129.40, 132.33, 134.84, 203.27; IR ¯ = 1676 cm
(C=O); Anal. Calcd for C16H24OS2: C, 64.82; H, 8.16%. Found:
C, 64.80; H, 7.89%.
X-ray crystal data and structure refinement for 6a. Crystal data
for C16H24OS2. FW 296.47, Monoclinic, space group: P21/c,
a = 6.8289(17) ¡, b = 15.395(4) ¡, c = 16.041(4) ¡, ¡ = 90°,
¢ = 94.953(3)°, £ = 90°, V = 1680.2(7) ¡3, Z = 4, Dcalcd
=
1.172 Mg m¹3, ® (Mo K¡) = 0.414 mm¹1, the final R and wR
were 0.0474 and 0.1354, respectively, using 9657 reflections.
Pd1-S2, P1-Pd1-P2, and S1-Pd1-P1 is ca. 360°, suggesting
that complex 11 has planar structure (also see Supporting
Information; Table S14).
The bond lengths and angles of the five-membered ring of 9
are similar to those of 11. The bond lengths of Pt-P (2.2870 and
2.3110 ¡) in 9 are shorter than those of Pd-P (2.3170 and
2.3547 ¡) in 11.
In summary, synthesis of ¡-thiolactone 4a by reacting 1,2-
dithietan-3-one 2a with triphenylphosphine was achieved. The
reaction of 2a with Grignard reagents gave 2-mercapto-2-
methylpropanethioates 6. Reaction of 2a with (©2-ethylene)-
bis(triphenylphosphine)platinum(0) (8) gave a novel thiolato
thiocarboxylato-platinum complex 9 in high yield. Thiolato
thiocarboxylato-palladium complex 11 was obtained in a
similar manner.
1
6b; colorless oil; H NMR (CDCl3, 400 MHz): ¤ 1.25 (s, 18H),
2.17 (s, 4H, Me + SH); 13C NMR (CDCl3, 100 MHz): ¤ 15.07,
¹1
30.71, 41.91, 79.87, 205.04; IR ¯ = 1667 cm (C=O); Anal.
Calcd for C11H22OS2: C, 56.36; H, 9.46%. Found: C, 56.64; H,
9.24%.
6c; colorless crystals; mp ¯30 °C; 1H NMR (CDCl3, 400 MHz):
¤ 1.26 (s, 18H), 1.27 (s, 3H), 1.29 (s, 3H), 2.14 (s, 1H), 3.33-3.40
(m, 1H); 13C NMR (CDCl3, 100 MHz): ¤ 22.58, 30.87, 36.96,
¹1
42.10, 79.64, 204.41; IR ¯ = 1661 cm (C=O); Anal. Calcd for
C13H26OS2: C, 59.49; H, 9.98%. Found: C, 59.15; H, 9.95%.
Synthesis of Platinum Complex 9.
To a solution of 2a
(0.011 g, 0.050 mmol) in dichloromethane (2 mL) was added
(©2-ethylene)bis(triphenylphosphine)platinum(0) (8) (0.037 g,
0.050 mmol). After stirring for 10 min, the reaction mixture
was evaporated to give a black-yellow solid. The residue
was recrystallized from acetonitrile-chloroform (2:1) to give 9
(0.044 g, 0.047 mmol). Compound 9; yellow crystals; mp 266-
272 °C (dec.); 1H NMR (CDCl3, 400 MHz): ¤ 1.15 (s, 18H), 7.10-
7.52 (m, 30H); 13C NMR (CDCl3, 100 MHz): ¤ 30.51, 43.25
Experimental
General.
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 on
silica (Merck, 70-230 mesh). NMR spectra (1H at 400 MHz, 13C
at 100 MHz, 31P at 162 MHz, and 195Pt at 86 MHz) were recorded
in CDCl3, and chemical shifts are expressed in ppm relative to
internal TMS for 1H and 13C, and external Na2PtCl6 (D2O) for
195Pt NMR. Melting points were uncorrected. Synthesis of 1,2-
dithietan-3-one 2a and ¡-thiolactone 4a was shown in a previous
communication.
Synthesis of 1,2-Dithietan-3-one 2b. 1,2-Dithietan-3-one 2b
was synthesized in a similar manner according to the previous
communication.10 To a solution of 3b (0.086 g, 0.40 mmol) and
ethyl chlorooxyimidoacetate (0.066 g, 0.43 mmol) in THF (1.0 mL)
was added a solution of triethylamine (0.048 g, 0.48 mmol) in THF
(1.0 mL) in one portion at room temperature. After being stirred for
2 h, the reaction mixture was filtered and evaporated to give yellow
oily crystals, which were chromatographed over silica gel by
elution with hexane to give pure 2b (0.078 g, 0.32 mmol). 2b:
(JP-C = 18.3 Hz), 71.40 (JP-C = 4.2 Hz), 127.66 (meta-Ph, JP-C
=
10.4 Hz), 127.97 (meta-Ph, JP-C = 10.4 Hz), 129.84 (ipso-Ph,
J
J
P-C = 54.9 Hz), 130.44-130.46 (br, para-Ph), 131.02 (ipso-Ph,
P-C = 54.6 Hz), 134.78-135.52 (m, ortho-Ph), 221.90 (JPt-C
=
20.7 Hz); 31P NMR (CDCl3, 162 MHz): ¤ 19.3 (JPt-P = 2846 Hz,
J
P-P = 27 Hz), 26.0 (JPt-P = 3013 Hz, JP-P = 27 Hz); 195Pt NMR
(CDCl3, 86 MHz, Na2PtCl6): ¤ ¹4745 (JPt-P = 2846, 3011 Hz); IR
¯ = 1090 (S=O), 1607 (C=O), and 424 (Pt-S) cm¹1; Anal. Calcd
for C46H48OP2PtS2¢H2O: C, 57.79; H, 5.27%. Found: C, 57.65, H,
4.98%. Single crystals of 9 were recrystallized from its acetonitrile
solution.
X-ray crystallographic data for 9: crystal data for C48H51NO-
ꢀ
P2S2Pt. FW 979.05, Triclinic, space group: P1, a = 10.9455(4),
b = 12.8134(5), c = 18.0138(7) ¡, ¡ = 91.4058(4)°, ¢ =
107.0700(4)°, £ = 114.2731(4)°, V = 2170.84(14) ¡3, Z = 2,
D
calcd = 1.498 Mg m¹3, ® (Mo K¡) = 0.414 mm¹1, the final R
and wR were 0.0243 and 0.0738, respectively, using 25867
reflections.

T. Shigetomi et al.
Bull. Chem. Soc. Jpn. Vol. 82, No. 7 (2009)
859
Synthesis of Palladium Complex 11. To a solution of 2a
(0.022 g, 0.10 mmol) in dichloromethane (2 mL) was added
tetrakis(triphenylphosphine)palladium(0) (10) (0.037 g, 0.050
mmol). After stirring for 10 min, the reaction mixture was evapo-
rated to give a black-yellow solid. The residue was recrystallized
from acetonitrile-chloroform (2:1) to give 11 (0.044 g, 0.047
mmol). 11; reddish yellow crystals; mp 211.0-222.2 °C (dec.);
1H NMR (CDCl3, 400 MHz): ¤ 1.16 (s, 18H), 7.16-7.47 (m, 30H);
6
a) G. Pattenden, A. J. Shuker, Tetrahedron Lett. 1991, 32,
6625. b) Y. Kanda, H. Saito, T. Fukuyama, Tetrahedron Lett. 1992,
33, 5701. c) G. Pattenden, A. J. Shuker, J. Chem. Soc., Perkin.
Trans. 1 1992, 1215.
7
a) K. Mitra, W. Kim, J. S. Daniels, K. S. Gates, J. Am.
Chem. Soc. 1997, 119, 11691. b) S. Wu, A. Greer, J. Org. Chem.
2000, 65, 4883. c) S. J. Behroozi, W. Kim, J. Dannaldson, K. S.
Gates, Biochemistry 1996, 35, 1768.
13C NMR (CDCl3, 100 MHz): ¤ 30.63, 42.84, 75.84 (JP-C
6.7 Hz), 127.89 (meta-Ph, JP-C = 10.4 Hz), 128.24 (meta-Ph,
P-C = 10.4 Hz), 130.31 (ipso-Ph, P-C = 43.9 Hz), 130.36-
=
8
a) T. Shigetomi, A. Nojima, K. Shioji, K. Okuma, Y.
Yokomori, Heterocycles 2006, 68, 2243. b) K. Okuma, A. Nojima,
Y. Yokomori, Heterocycles 2008, 75, 1417.
J
J
130.39 (br, para-Ph), 131.46 (ipso-Ph, JP-C = 40.9 Hz), 134.76
(ortho-Ph, JP-C = 12.3 Hz), 135.07 (ortho-Ph, JP-C = 12.3 Hz),
220.27; 31P NMR (CDCl3, 162 MHz): ¤ 24.5 (JP-P = 52.2 Hz),
32.6 (JP-P = 52.2 Hz); IR ¯ = 1607 (C=O). Anal. Calcd for
C46H48OP2PdS2¢H2O: C, 63.70; H, 5.81%. Found: C, 63.40, H,
5.63%. Single crystals of 11 were obtained from its acetonitrile
solution.
9
T. Shigetomi, K. Okuma, Y. Yokomori, Tetrahedron Lett.
2008, 49, 36.
10 K. Shioji, A. Matsumoto, M. Takao, Y. Kurauchi, T.
Shigetomi, Y. Yokomori, K. Okuma, Bull. Chem. Soc. Jpn. 2007,
80, 743.
11 E. Schaumann, U. Behrens, Angew. Chem., Int. Ed. Engl.
1977, 16, 722.
X-ray crystallographic data for 11: crystal data for C48H51-
NOP2PdS2. FW 890.36, Triclinic, space group: P1, a =
10.9854(10) ¡, b = 12.8425(11) ¡, c = 18.0120(16) ¡, ¡ =
12 M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria,
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C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill,
B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, J. A. Pople,
Gaussian 03, Revision E.01, Gaussian, Inc., Wallingford CT, 2004.
13 W. Weigand, R. Wünsch, Chem. Ber. 1996, 129, 1409; W.
Weigand, R. Wünsch, K. Polborn, G. Mloston, Z. Anorg. Allg.
Chem. 2001, 627, 1518; R. Wünsch, W. Weigand, G. Nuspl,
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2004, 10, 1666; J. Vicente, P. González-Herrero, Y. Garcia-
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Vicente, P. González-Herrero, M. Pérez-Cadenas, P. G. Jones, D.
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ꢀ
91.4570(10)°, ¢ = 107.0700(10)°, £ = 114.2710(10)°, V =
¹3
2183.1(3) ¡3, Z = 2, Dcalcd = 1.354 Mg m ® (Mo K¡) = 0.414
,
mm¹1, the final R and wR were 0.0497 and 0.1465, respectively,
using 26182 reflections.
Crystallographic data have been deposited with Cambridge
Crystallographic Data Centre. Deposition numbers CCDC-726799
for compound 6a, and CCDC-726800 for Pt complex 9, and
CCDC-726801 for Pd complex 11. Copies of the data can be
obtained free of charge via http://www.ccdc.cam.ac.uk/conts/
retrieving.html or from the Cambridge Crystallographic Centre,
12, Union Road, Cambridge, CB2 1EZ, U.K.; Fax +44 1233
336033; e-mail: deposit@ccdc.cam.ac.uk).
Supporting Information
Bond lengths and bond angles of 2b, 6a, 9, and 11.
Theoretically optimized coordinate of 2a. Observed and calculated
structural parameters of 2a and 2b. Distance from a least-squares
plane of complex 9 and 11. This material is available free of charge
on the Web at: http://www.csj.jp/journals/bcsj/.
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