᎐
᎐
᎐
᎐
᎐
Table 3 Summary of crystal structure data for complexes 5 and 7
trans-[Ph(Et P) Pt–C᎐CSC᎐CC᎐CSC᎐C–Pt(PEt ) Ph] 6. To
᎐
᎐
᎐
3
2
᎐
3 2
᎐
᎐
᎐
a mixture of HC᎐CSC᎐CC᎐CSC᎐CH (13.0 mg, 0.08 mmol)
᎐
᎐
᎐
᎐
5
7
and 2 equivalents of trans-[PtPh(Cl)(PEt3)2] (87.0 mg, 0.16
mmol) in CH2Cl2–(Me3Si)2NH (18 cm3, 1:1 v/v) was added CuI
(3 mg). The solution was stirred at room temperature over
20 h, after which all volatile components were removed under
reduced pressure. The product was purified on preparative TLC
plates with hexane–CH2Cl2 (1:1, v/v) as eluent, affording com-
pound 6 as a viscous oil (49.0 mg, 52%). IR (KBr): 2067 and
Empirical formula
M
C40H70P4Pt2S
1097.08
C38H54N2PtS2Si2
854.24
Crystal system
Space group
a/Å
b/Å
c/Å
α/Њ
β/Њ
Monoclinic
P21/n (no. 14)
21.205(4)
9.053(2)
24.430(5)
Triclinic
P1 (no. 2)
¯
7.906(1)
14.018(1)
19.069(1)
98.66(1)
92.38(1)
97.83(1)
2065.6(3)
2
2033 cmϪ1 (νC᎐C). 1H NMR (CDCl3): δ 1.04 (m, 36 H, CH3), 1.64
᎐
(m, 24 H, CH2), 6.77 (m, 2 H, Hpara of Ph), 6.92 (m, 4 H, Hmeta
of Ph) and 7.24 (m, 4 H, Hortho of Ph). 13C-{1H} NMR (CDCl3):
95.67(3)
γ/Њ
᎐
δ 7.96, 14.93 (C H ), 73.22, 73.25, 77.20, 81.28 (C᎐C), 121.47,
᎐
2
5
U/Å3
4667(2)
4
61.95
127.36, 138.91 and 154.45 (Ph). 31P-{1H} NMR (CDCl3):
δ 11.11 (1JPt-P = 2616 Hz). FAB mass spectrum: m/z 1177 (Mϩ).
UV/VIS (CH2Cl2): λmax (ε × 10Ϫ4 dm3 molϪ1 cmϪ1)/nm 263 br
(2.1) and 318 (0.7). Emission (CH2Cl2, λexcitation = 288 nm): 340
nm. Microanalytical data are not available due to the instability.
Z
µ(Mo-Kα)/cmϪ1
35.68
No. reflections collected
26410
10473 (0.033)
22607
Unique reflections (Rint
)
3228 (0.045)
2139 (n = 1.5)
R = 0.056
Rw = 0.060
Observed reflections [I > nσ(I)] 10473 (n = 2.0)
Residuals
R = 0.0291
wR2 = 0.0845
᎐
᎐
᎐
cis-[Pt(Me bipy){C᎐CSC᎐C(TIPS)} ]
[Pt(Me bipy)Cl ] (100.0 mg, 0.22 mmol), HC᎐CSC᎐C(TIPS)
7.
Compounds
᎐
2
2
᎐
᎐
᎐
᎐
2
2
(158.5 mg, 0.67 mmol) and CuI (3 mg) were stirred together
in a mixture of CH2Cl2 (25 cm3) and NHPri2 (3 cm3) for 24 h.
The volatile portion was evaporated under vacuum, the residue
dissolved in the minimum amount of CH2Cl2 and passed
through a short column (5 cm) of silica gel with hexane–CH2Cl2
as eluent. Evaporation of the solvent yielded complex 7 as a
bright yellow solid in 74% yield (140.0 mg). IR (KBr): 2088 and
2057 cmϪ1 (νC᎐C). 1H NMR (CDCl3): δ 1.11 (m, 42 H, Pri), 2.64
(s, 6 H, CH3)᎐, 6.94 (d, 2 H, J = 5.7, pyridyl H), 8.01 (s, 2 H,
pyridyl H) and 8.48 (d, 2 H, J = 5.7 Hz, pyridyl H). 13C-{1H}
Acknowledgements
We thank the Hong Kong Research Grants Council (RGC/97-
98/48, HKBU 2048/97P) and Hong Kong Baptist University
(A. W. M. L. and W.-Y. W.) for financial support.
References
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᎐
94.43, 97.65 (C᎐C), 125.27, 127.30, 148.97, 151.64 and 155.53
᎐
(pyridyl C). FAB mass spectrum: m/z 853 (Mϩ). UV/VIS
(CH2Cl2): λmax (ε × 10Ϫ4 dm3 molϪ1 cmϪ1)/nm 283 br (1.7) and
413 (0.5). Emission (CH2Cl2, λexcitation = 410 nm): 589 nm. Calc.
for C38H54N2PtS2Si2: C, 53.43; H, 6.37; N, 3.28. Found: C,
53.08; H, 6.15; N, 3.20%.
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Crystallography
Colourless crystals of complex 5 and yellow crystals of complex
7 suitable for X-ray diffraction studies were grown by evapor-
ation of their respective solutions in hexane–CH2Cl2. Geometric
and intensity data were collected at 273 K using graphite-
monochromated Mo-Kα radiation (λ = 0.71073 Å) on a Bruker
SMART CCD area-detector (5) and MAR research image plate
scanner (7). Cell parameters and the orientation matrix for 5
were obtained from the least-squares refinement of reflections
measured in three different sets of 15 frames each. The collected
frames were processed with the software SAINT21a and an
absorption correction was applied (SADABS21b
) to the
collected reflections. For 7 65 × 3Њ frames with an exposure time
of 5 min per frame were used for data acquisition and inter-
frame scaling was employed for the absorption correction.
The space groups of each crystal were determined from the
systematic absences and Laue symmetry check and confirmed
by successful refinement of the structure. The structures of
complexes 5 and 7 were solved by direct methods (SHELXTL22
for 5, SHELXS 8623 for 7) in conjunction with standard Fourier
difference techniques and subsequently refined by full-matrix
least-squares analyses. All non-hydrogen atoms were assigned
anisotropic displacement parameters. In each case, hydrogen
atoms were generated in their idealized positions (C–H, 0.95 Å)
and allowed to ride on the respective carbon atoms. Crystal-
lographic and other experimental details are collected in
Table 3.
8 W. Wong, T. Bartik, M. Brady, B. Bartik, J. A. Ramsden, A. M.
Arifand and J. A. Gladysz, J. Am. Chem. Soc., 1995, 117, 11922;
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10 A. W. M. Lee, A. B. W. Yeung, M. S. M. Yuen, H. Zhang, X. Zhao
and W. Y. Wong, Chem. Commun., 2000, 75.
CCDC reference number 186/2152.
lographic files in .cif format.
J. Chem. Soc., Dalton Trans., 2000, 3675–3680
3679
Zhang, Hongkui
