Synthesis, Structure, and 31P NMR of Sulfur/Oxygen-Bridged Incomplete Cubane-Type Molybdenum and Tungsten Clusters with Triphenylphosphine Ligands |
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Authors: | Mari Sasaki Genta Sakane Tadashi Ouchi Takashi Shibahara |
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Institution: | (1) Department of Chemistry, Okayama University of Science, 1-1 Ridai-cho, Okayama, 700, Japan;(2) Analytical Research Laboratories, Fujisawa Pharmaceutical Co., Ltd., 1-6, 2-chome, Kashima, Yodogawa-ku, Osaka, 532, Japan |
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Abstract: | Sulfur/oxygen-bridged incomplete cubane-type triphenylphosphine molybdenum and tungsten-clusters Mo3S4Cl4(H2O)2(PPh3)3]·3THF (1A), Mo3S4Cl4(H2O)2(PPh3)3]·2THF (2A), Mo3OS3Cl4(H2O)2(PPh3)3]·2THF (1B), and W3S4Cl4(H2O)2(PPh3)3]·2THF (1C) were prepared from the corresponding aqua clusters and PPh3 in THF/MeOH. On recrystallization from THF, procedures with and without addition of hexane to the solution gave 1A and 2A, respectively, while the procedures gave no effect on the formation of 1B and 1C. Crystallographic results obtained are as follows: 1A: monoclinic, P21/n, a=17.141(4) Å, b=22.579(5) Å, c=19.069(4) Å, =96.18(2)°, V=7337(3) Å3, Z=4, R(R
w)=0.078(0.102); 1C: monoclinic, P2
1/c, a=12.635(1) Å, b=20.216(4) Å, c=27.815(3) Å, =96.16(1)°, V=7062(2) Å3, Z=4, R(R
w)=0.071(0.083). If the phenyl groups are ignored, the molecule Mo3S4Cl4(H2O)2(PPh3)3] in 2A has idealized CS symmetry with the mirror plane perpendicular to the plane determined by the metal atoms, while the molecule in 1A does not have the symmetry. The tungsten compound 1C is isomorphous with the molybdenum compound 2A. 31P NMR spectra of 1A, 2A, and 1C were obtained and compared with similar clusters with dmpe (1,2-bis(dimethylphosphino)ethane) ligands. |
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Keywords: | Mo3S4 Mo3OS3 W3S4 PPh3 incomplete cubane-type |
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