Chemistry Letters Vol.32, No.2 (2003)
171
(2002).
5
6
Very recently, Nakayama and Ishii et al. have synthesized the disulfur
monoxide complex [(PPh3)2PtS2O] through the reaction of cyclic poly-
sulfides S-oxide(s) with [(PPh3)2Pt(C2H4)]; M. Murata, A. Ishii, and J.
Nakayama, at the 81st Annual Meeting of the Chemical Society of Japan,
March 2002, Abst., No. 4B334.
2a: mp 175.0–176.5 ꢂC; 1H NMR (300 MHz, CDCl3): d 0.13 (s, 18H), 0.14
(s, 18H), 0.15 (s, 18H), 0.18 (s, 18H), 0.22 (s, 54H), 1.94 (d, 2JPH ¼ 7:5 Hz,
2
2
3H), 2.10 (d, JPH ¼ 8:0 Hz, 3H), 2.14(d, JPH ¼ 8:2 Hz, 3H), 2.24(d,
2JPH ¼ 8:9 Hz, 3H), 3.06 (d, JPH ¼ 2:5 Hz, 2H), 3.14(d, JPH ¼ 2:9 Hz,
4
4
4
2H), 6.68 (d, JPH ¼ 3:1 Hz, 4H); 31P{1Hg NMR (120 MHz, CDCl3): d
1
2
1
ꢁ29:7 (d, JPtP ¼ 4263 Hz, JPP ¼ 8 Hz), ꢁ32:8 (d, JPtP ¼ 3254 Hz,
2JPP ¼ 8 Hz); 195Pt{1Hg NMR (64MHz, CDCl 3): d ꢁ4708 (dd, JPPt
¼
1
3254, 4263 Hz); IR (KBr): ꢀ (SO) = 1042 cmꢁ1; UV-vis (CH2Cl2): 379 nm
(sh, " ¼ 2640). FAB MS, m=z: 1645 (M+H)þ, 1629 (MꢁO+H)þ; Anal.
Calcd for C64H146OP2PtS2Si14: C, 46.69; H, 8.94. Found: C, 46.53; H, 9.11.
2b: mp 158.2–159.5 ꢂC; 1H NMR (300 MHz, CDCl3): d 0.12 (s, 36H), 0.13
(s, 18H), 0.17 (s, 18H), 0.20 (s, 54H), 1.99 (d, 2JPH ¼ 7:5 Hz, 3H), 2.10 (d,
Figure 1. ORTEP drawing of 3 with thermal elꢂlipsoid plot (50%
ꢀ
probability). Selected bond distances (A) and angles ( ): Pt1–O1 2.21(3),
Pt1–P1 2.263(16), Pt1–S1 2.312(16), O1–S2 1.54(3), S1–S2 2.079(13), S2–
O2 1.43(2), S2–O3 1.43(2); P1–Pt1–P1ꢀ 105.4(2), O1–Pt1–S1 77.3(6), Pt1–
O1–S2 98.1(15), Pt1–S1–S2 81.3(5), O1–S2–S1 101.4(10).
2JPH ¼ 8:0 Hz, 3H), 2.14(d, JPH ¼ 8:2 Hz, 3H), 2.24(d, JPH ¼ 8:9 Hz,
2
2
3H), 3.06 (s, 2H), 3.18 (s, 2H), 6.66 (s, 4H); 31P{1Hg NMR (120 MHz,
1
2
CDCl3):
1JPPt ¼ 3974 Hz, 2JPP ¼ 12 Hz); 77Se{1Hg NMR (57 MHz, CDCl3, 25 ꢂC):
d 689, 1135 (1JPtSe ¼ 416 Hz); 195Pt{1Hg NMR (64MHz, CDCl 3): d ꢁ4768
d ꢁ34:8 (d, JPtP ¼ 3431 Hz, JPP ¼ 12 Hz), ꢁ38:7 (d,
which are comparable with those of 1b (d = ꢁ44:1,
1JPtP ¼ 3865 Hz), therefore, the PtSeO3 moiety in 6 has pre-
sumably a mirror plane vertical to the PtP2 plane as the PtSe2 ring
in the complex 1b. In the 77Se NMR spectrum, only one resonance
was observed at lower field (d = 1504) than those of 2b (d = 689,
1135) and 1b (d = 582), although the satellite peaks due to the
77Se–195Pt couplings could not be found. The 195Pt NMR signal
was observed at d = ꢁ3176, but such a large low field shift in
comparison to those of 2b (d = ꢁ4768) is not observed for the
conversion of 1b (d = ꢁ5030) to 2b. Since the 195Pt resonance
usually moves to lower field in the order of O > S > Se > Te for
some platinum complexes having Group 16 elements as the
coordinated atoms of the ligands,13 coordination of the SeO3
ligand in 6 should be considered to have the O-bound geometry
rather than Se-bound one. On the basis of these results, we can
describe the geometry of 6 as the structure with the chelating O,O-
bound geometry.14
1
(dd, JPPt ¼ 3431, 3974Hz); UV-vis (CH 2Cl2): 392 nm (" ¼ 1700); FAB
MS m=z: 1739 ðMÞþ, 1723 (MꢁO)þ; Anal. Calcd for C64H146OP2PtSe2Si14
:
C, 44.18; H, 8.46. Found: C, 44.27; H, 8.59.
I.-P. Lorenz and J. Kull, Angew. Chem., Int. Ed. Engl., 25, 261 (1986).
7
8
9
G. Schmid, G. Ritter, and T. Debaerdemaeker, Chem. Ber., 108, 3008 (1975).
3: mp 220.6–221.1 ꢂC (decomp.); 1H NMR (300 MHz, CDCl3): d 0.17 (s,
2
36H), 0.19 (s, 36H), 0.22 (s, 54H), 2.05 (d, JPH ¼ 9:1 Hz, 6H), 2.19 (d,
2JPH ¼ 9:5 Hz, 6H), 3.01 (s, 2H), 3.42 (s, 2H), 6.67 (d, 4JPH ¼ 3:8 Hz, 2H),
6.70 (d, 4JPH ¼ 3:6 Hz, 2H); 31P{1Hg NMR (120 MHz, CDCl3): d ꢁ31:5 (d,
1JPtP ¼ 3240 Hz, 2JPP ¼ 21 Hz), ꢁ48:1 (d, 1JPtP ¼ 4137 Hz, 2JPP ¼ 21 Hz);
195Pt{1Hg NMR (64MHz, CDCl 3): d ꢁ3995 (dd, 1JPPt ¼ 3240, 4137 Hz).
FAB MS m=z: 1677 (M+H)þ; Anal. Calcd for C64H146O3P2PtS2Si14: C,
45.80; H, 8.77. Found: C, 45.74; H, 8.80. 4: mp 178.8–180.4 ꢂC (decomp.);
1H NMR (300 MHz, CDCl3): d 0.12 (s, 18H), 0.16 (s, 18H), 0.18 (s, 18H),
0.19 (s, 18H), 0.25 (s, 27H), 0.26 (s, 27H), 1.78–1.96 (m, 12H), 2.48 (s, 1H),
2.73 (s, 2H), 3.16 (s, 1H), 4.00 (s, 1H), 6.65–6.74 (m, 4H); 31P{1Hg NMR
(120 MHz, CDCl3): d ꢁ9:97 (1JPtP ¼ 2683 Hz); 195Pt{1Hg NMR (64MHz,
CDCl3):
d
ꢁ4263 (t, 1JPPt ¼ 2683 Hz); Anal. Calcd for
C64H147ClOP2PtSi14: C, 47.49; H, 9.15. Found: C, 47.63; H, 9.25. The
existence of the chlorine atom in 4 was confirmed by X-ray fluorescence
Thus, the S2O and Se2O complexes 2a,b here obtained have
shown different reactivities toward an excess of oxidant.
Although the mechanism of both unusual reactions has been
unclear at present, attempts to characterize and isolate the
intermediates are currently in progress.
spectroscopy.
10 Crystallographic data for 3: C64H146O3P2PtS2Si14, M ¼ 1678:22, mono-
ꢀ
clinic, space group C2=c, a ¼ 39:77ð2Þ, b ¼ 9:320ð5Þ, c ¼ 23:870ð13Þ A;
ꢀ 3
ꢁ ¼ 90:921ð11Þꢂ; V ¼ 8847ð8Þ A ; Z ¼ 4; ꢂcalcd ¼ 1:260 g cmꢁ3
,
ꢃ ¼ 19:0 cmꢁ1, R1 ¼ 0:108 (I > 2ꢄðIÞ), wR2 ¼ 0:216 (all data) for 7753
observed reflections and 477 variable parameters, T ¼ 93ð2Þ K, GOF = 1.28.
Since there is the disorder of two sets of PtS2O3 units, which are overlapped
each other by the C2 symmetry operation, with occupancies of 0.5 and 0.5,
the structure of 3 was best solved as a molecular having pseudo 2-fold
symmetry in space group C2=c with Z ¼ 4. The attempts to solve the
structure in space group Cc with Z ¼ 4 did not give better results compared
to the above one. Two sets of three methyl carbons of the two trimethylsilyl
group on the Bbt group are also disordered. In Figure 1, another part of the
disoredered carbons and one PtS2O3 core are omitted to avoid confusion. All
non-hydrogen atoms were refined anisotropically.
This work was partially supported by Grants-in-Aid for
Scientific Research (Nos. 12CE2005, 11166250, and 14078213)
from Ministry of Education, Culture, Sports, Science, and
Technology of Japan.
References and Notes
1
2
3
For reviews on transition metal oxopolychalcogenido complexes, see: W.
Weigand and R. Wunsch, Chem. Ber., 129, 1409 (1996); W. A. Scenk,
11 Examples of O,S-coordinated thiosulfate complex: A. Z. Rys, A.-M. Lebuis,
A. Shaver, and D. N. Harpp, Inorg. Chem., 41, 3653 (2002); G. J. Kubas and
R. R. Ryan, Inorg. Chem., 23, 3181 (1984); M. L. H. Green, A. H. Lynch, and
M. G. Swanwick, J. Chem. Soc., Dalton Trans., 1972, 1445.
¨
Angew. Chem., Int. Ed. Engl., 26, 98 (1987).
M. E. Raseta, S. A. Cawood, M. E. Welker, and A. L. Rheingold, J. Am.
Chem. Soc., 111, 8268 (1989); G. A. Urove and M. E. Welker,
Organometallics, 7, 1013 (1988).
12 6: mp 222.4–223.8 ꢂC (decomp.); 1H NMR (300 MHz, CDCl3): d 0.18 (s,
2
4
72H), 0.20 (s, 54H), 1.98 (t, AA’X spin system, 1=2½ JPH þ JPHꢃ ¼ 9:3 Hz,
12H), 3.49 (s, 4H), 6.66 (s, 4H); 31P{1Hg NMR (120 MHz, CDCl3): d ꢁ41:7
(1JPtP ¼ 3639 Hz); 77Se{1Hg NMR (57 MHz, CDCl3, 25 ꢂC): d 1504;
A. Z. Rys, A.-M. Lebuis, A. Shaver, and D. N. Harpp, Organometallics, 18,
1113 (1999); M. A. Halcrow, J. C. Huffman, and G. Christou, Inorg. Chem.,
33, 3639 (1994); M. Herberhold, B. Schmidkonz, M. L. Ziegler, and T. Zahn,
Angew. Chem., Int. Ed. Engl., 24, 515 (1985); J. E. Hoots, D. A. Lesch, and T.
B. Rauchfuss, Inorg. Chem., 23, 3130 (1984); J. E. Hoots, T. B. Rauchfuss,
and S. R. Wilson, J. Chem. Soc., Chem. Commun., 1983, 1226; A. P.
Ginsberg, W. E. Lindsell, C. R. Sprinkle, K. W. West, and R. L. Cohen,
Inorg. Chem., 21, 3666 (1982); G. Schmid and G. Ritter, Angew. Chem., Int.
Ed. Engl., 14, 645 (1975).
1
195Pt{1Hg NMR (64MHz, CDCl 3): d ꢁ3176 (t, JPPt ¼ 3639 Hz); HRMS
m=z calcd for C64H146O3P2PtSeSi14: 1691.6330, found 1691.6316; Anal.
Calcd for C64H146O3P2PtSeSi14: C, 45.40; H, 8.69. Found: C, 45.29; H, 8.67.
13 P. S. Pregosin, Coord. Chem. Rev., 44, 247 (1982).
14Only one example of an O,O-coordinated selenite complex [(PPh 3)2PtSeO3]
has been reported: G. R. Hughes, P. C. Minshall, and D. M. P. Mingos, J.
Less-Common Met., 116, 199 (1986).
4K. Nagata, N. Takeda, and N. Tokitoh,
Angew. Chem., Int. Ed., 41, 136