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Formation of group 14 and 15 heteroatom derivatives of trinuclear [M3Se4(H2O)9]4+ (M = Mo, W) and the decreased reactivity of [W3S4(H2O)9]4+

Lookup NU author(s): Dr Mark Elsegood, Emeritus Professor Bill Clegg, Emeritus Prof Alfred Sykes


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Group 14 and 15 elements (M′ = Pb, As, Sb, Bi), which are known to form corner-shared double cube derivatives [Mo6M′S8(H2O)18] 8+ of [Mo3S4(H2O)9]4+, are here shown to react with [M3Se4(H2O)9]4+ (M = Mo, W). Using similar procedures, no corresponding derivatives of [W3S4(H2O)9]4+ are obtained. ICP-AES metal analyses on the [M3Se4(H2O)9]4+ products, together with stoichiometries for oxidation with the CoIII oxidant [Co(dipic)2]-, are consistent with corner-shared double cube formulae [M6M′Se8(H2O)18] 8+. UV-Vis spectra are reported as part of the characterisation, and observations are made on the reactivity of the cubes with O2. The X-ray crystal structures of [Mo3Se4(H2O)9](pts)4 ·10H2O, [W3Se4(H2O)9](pts)4 ·12H2O and one of the key products [Mo6AsSe8(H2O)18] (pts)8·8H2O have been determined (pts- = p-toluenesulfonate). Whereas differences in reactivity of [Mo3Se4(H2O)9]4+ and [W3Se4(H2O)9]4+ are small, the differences for [Mo3S4(H2O)9]4+ are much more marked. In the context of heteroatom incorporation the incomplete cube [W3S4(H2O)9]4+ is by far the least reactive of the four trinuclear clusters.

Publication metadata

Author(s): Hernandez-Molina R, Elsegood MRJ, Clegg W, Sykes AG

Publication type: Article

Publication status: Published

Journal: Journal of the Chemical Society, Dalton Transactions

Year: 2001

Issue: 14

Pages: 2173-2178

Print publication date: 01/01/2001

ISSN (print): 1477-9226

ISSN (electronic): 1477-9234

Publisher: Royal Society of Chemistry


DOI: 10.1039/b101399h


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