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DOI: 10.1039/A701168G (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 1753-1758

Structural diversity of tetranuclear tungsten sulfide clusters: syntheses and crystal structures of clusters containing raft-type W4(µ3-S)2(µ-S)4 and tetrahedral W4(µ-S)6 cores

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Shigeki Kuwata, Yasushi Mizobe and Masanobu Hidai

Abstract

Reaction of cis-[W(N2)2(PMe2Ph)4 ] 1 with 2 equivalents of (Me3Si)2S in the presence of an excess of MeOH gave a tetranuclear tungsten sulfide cluster [W4(µ3-S)2(µ-S)4(SH) 2(PMe2Ph)6] 2. Substitution of chloride anions for the terminal SH ligands in 2 took place on reaction with 1 equivalent of SnCl2, giving the isostructural W4 cluster [W4(µ3-S)2(µ-S)4Cl 2(PMe2Ph)6] 3. Both 2 and 3 with ten skeletal electrons consist of an almost equilateral raft-type W4 framework with five metal–metal bonds. On treatment with 2.4–3 equivalents of AgOSO2CF3, compound 3 underwent two-electron oxidation to give [W4(µ3-S)2(µ-S)4Cl 2(PMe2Ph)6][OSO2CF3 ]24, which has a distorted raft-type W4 core owing to the presence of only eight skeletal electrons. On the other hand, reduction of 3 with an excess of Na/Hg resulted in formation of the twelve-skeletal-electron cluster [W4(µ-S)6(PMe2Ph)4] 5 containing a tetrahedral W4 core with six W–W bonds. The detailed structures of 2–5 were determined by single-crystal X-ray diffraction.

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