SHORT COMMUNICATION
bis(1,4-phenyldiethynylene)platinum(II) (1a, 34 mg, 0.05 mmol)
were added to a small double-neck flask, and the resulting mixture
was stirred to reflux for 24 h at 90 °C. Evaporation of the solvent
under reduced pressure gave a solid residue. The crude product was
purified by column chromatography, and 2a was obtained as a yel-
low solid.
refined anisotropically. Hydrogen atoms were refined with the ri-
ding model. The final cycle was subjected to full-matrix least-
squares refinement (SHELXL-97)[20] on F2. All calculations were
performed with the Crystal Structure[21] crystallographic software
package except for the refinement, which was performed with
SHELXL-97.[20]
2a: Yellow solid in 73% yield (41 mg). M. p.: 148–150 °C. 1H NMR
(400 MHz, CDCl3): δ = 7.08–7.49 (m, 30 H), 2.08–2.15 (m, 12 H,
-CH2-), 1.13–1.2 (m, 18 H, -CH3) ppm. 13C NMR (100 MHz,
CDCl3): δ = 8.23, 16.27, 109.43, 109.65, 125.71, 126.21, 126.46,
127.04, 127.43, 127.94, 128.19, 128.72, 128.85, 128.88, 129.12,
129.18, 129.23, 129.52, 129.56, 130.44, 130.54, 130.86, 134.94,
135.26, 135.36, 135.68 ppm. 31P NMR (161.83 MHz, CDCl3): δ =
Crystal Analysis Data for 2a: Empirical formula C56H60P2PtS4; FW
1118.37; yellow blocks, triclinic, primitive, space group P1 (#2); a
= 9.7254(3) Å, b = 11.3710(4) Å, c = 12.3853(4) Å, α = 74.1782(8)°,
β = 87.0192(8)°, γ = 77.5117(8)°, V = 1286.55(7) Å3, Rint = 0.0388,
R = 0.0449, wR = 0.1131, GOF = 1.116, Z = 1.
¯
CCDC-968717 contains the supplementary crystallographic data
for this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
11.62 (JPt,P = 2366 Hz), 11.67 (JPt,P = 2366 Hz) ppm. IR (KBr): ν
˜
= 3070, 3020, 2958, 2927, 2904, 2873, 2098, 1651, 1593, 1550, 1523,
1477, 1454, 1438, 817 cm–1. ESI-HRMS: m/z (%) = 1141.2467 (100)
[M + Na]+. FW: 1118.3651. C56H60P2PtS4 (1118.37): calcd. C
60.14, H 5.41; found C 60.28, H 5.42.
Acknowledgments
The other three complexes were synthesized similarly.
We thank the Nara Institute of Science and Technology for the use
of their facilities.
2b: Yellow solid in 82% (57.5 mg) yield. M. p.: 192–193 °C. 1H
NMR (400 MHz, CDCl3): δ = 7.72–7.76 (m, 12 H), 7.03–7.44 (m,
44 H), 6.13 (d, 4 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
125.45, 125.63, 127.36, 127.76, 127.90, 128.01, 128.71, 129.17,
129.50, 130.17, 130.45, 130.83, 131.23, 131.53, 134.74, 134.99,
[1] a) K. Sonogashira, Y. Fujikura, T. Yatake, N. Toyoshima, S.
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135.41 ppm. 31P NMR (161.83 MHz, CDCl3): δ = 19.23 (JPt,P
=
2639 Hz) ppm. IR (KBr): ν = 3051, 2985, 2102, 1577, 1546, 1527
˜
1477, 1434, 821 cm–1. ESI-HRMS: m/z (%) = 1429.2299 (100) [M
+ Na]+. FW: 1406.6219. C80H60P2PtS4 (1406.63): calcd. C 68.31, H
4.30; found C 68.18, H 4.42.
2c: Yellow solid in 55% (35 mg) yield. M. p.: 153–154 °C. 1H NMR
(400 MHz, CDCl3): δ = 6.92–7.67 (m, 38 H), 2.14–2.22 (m, 12 H,
-CH2-), 1.19–1.27 (m, 18 H, CH3) ppm. 13C NMR (100 MHz,
CDCl3): δ = 8.36, 16.37, 125.85, 126.35, 126.49, 126.63, 126.99,
127.14, 127.56, 128.05, 128.78, 128.91, 129.17, 129.28, 129.47,
129.60, 129.79, 130.59, 131.21, 136.66, 137.24 ppm. 31P NMR
(161.83 MHz, CDCl3): δ = 11.70 (JPt,P = 2370 Hz) ppm. IR (KBr):
ν = 3051, 3024, 2962, 2931, 2904, 2873, 2098, 1596, 1581, 1542,
˜
1485, 1438, 813 cm–1. ESI-HRMS: m/z (%) = 1293.3312 (100) [M
+ Na]+. FW: 1270.5570. C68H68P2PtS4 (1270.56): calcd. C 64.28, H
5.39; found C 64.55, H 5.81.
2d: Yellow solid in 49% (38 mg) yield. M. p.: 209–210 °C. 1H NMR
(400 MHz, CDCl3): δ = 7.78–7.84 (m, 12 H), 6.90–7.61 (m, 52 H),
6.29–6.31 (m, 4 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 125.42,
125.57, 125.84, 126.47, 126.92, 127.53, 127.81, 128.11, 128.87,
129.15, 129.26, 129.58, 129.86, 130.19, 130.58, 131.25, 131.38,
131.67, 135.09, 136.27, 140.12 ppm. 31P NMR (161.83 MHz,
[10] F.-R. Dai, Y.-C. Chen, L.-F. Lai, W.-J. Wu, C.-H. Cui, G.-P.
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CDCl3): δ = 19.31 (JPt,P = 2639 Hz) ppm. IR (KBr): ν = 3055,
˜
3024, 2106, 1581, 1542, 1481, 1434, 813 cm–1. ESI-HRMS: m/z (%)
= 1581.2714 (100) [M + Na]+. FW: 1558.8138. C92H68P2PtS4
(1558.83): calcd. C 70.89, H 4.40; found C 70.93, H 4.55.
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Single-Crystal X-ray Structure Determination for 2a
[13] A. L. Rieger, G. B. Carpenter, P. H. Rieger, Organometallics
1993, 12, 842.
A yellow block crystal of C56H60P2PtS4 having approximate dimen-
sions of 0.150ϫ0.120ϫ0.030 mm was mounted on a glass fiber.
All measurements were made with a Rigaku R-AXIS RAPID dif-
fractometer by using filtered Mo-Kα radiation. The data were col-
lected at a temperature of –150Ϯ1 °C to a maximum 2θ value of
55.00. A total of 192 oscillation images were collected. The expo-
sure rate was 24.0 sec/°. The crystal-to-detector distance was
127.40 mm. The structure was solved by direct methods[19] and ex-
panded by using Fourier techniques. The non-hydrogen atoms were
[14] a) M. S. Khan, M. R. A. Al-Mandhary, M. K. Al-Suti, N.
Feeder, S. Nahar, A. Kohler, R. H. Friend, P. J. Wilson, P. R.
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Soc. 2002, 124, 12412.
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