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DOI: 10.1039/A803396J (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1998, 2557-2562

Preparation, structure and properties of three [MoxW4–xS4(H2O)12]5+ (x = 1–3) and [MoW3Se4(H2O)12]5+ cuboidal complexes alongside [Mo4S4(H2O)12]5+ and [Mo4Se4(H2O)12]5+

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Iain J. McLean, Rita Hernandez-Molina, Maxim N. Sokolov, Mi-Sook Seo, Alexander V. Virovets, Mark R. J. Elsegood, William Clegg and A. Geoffrey Sykes

Abstract

The preparation of [MoW3S4(H2O)12]5+, [Mo2W2S4(H2O)12]5+, [Mo3WS4(H2O)12]5+ and [MoW3Se4(H2O)12]5+ from trinuclear incomplete cuboidal complexes [W3S4(H2O)9]4+, [MoW2S4(H2O)9]4+, [Mo2WS4(H2O)9]4+ and [W3Se4(H2O)9]4+ respectively has been achieved by reaction with [Mo2Cl8]4–. The structures of the 5+ cube [MoW3S4(H2O)12][pts]5·Hpts·16H2O (pts– = p-toluenesulfonate) and [Me2NH2]6[MoW3S4(NCS)12]·0.5H2O (6+ cube) have been determined by X-ray diffraction. Reversible behaviour is observed in cyclic voltammetry on the 5+ cubes, and reduction potentials (E[hair space]°′ vs. NHE) for the 6+/5+ and 5+/4+ couples have been determined. The cubes are more strongly reducing as the number of W atoms is increased with E[hair space]°′/mV values for [MoW3S4(H2O)12]6+/5+ (258), [MoW3S4(H2O)12]5+/4+ (–395) significantly smaller than values previously reported for [Mo4S4(H2O)12]6+/5+ (860) and [Mo4S4(H2O)12]5+/4+ (210). Peaks λ/nm (ε/M–1 cm–1 per cube) from UV/VIS/NIR spectra in 2.0 M Hpts shift from 635(435), 1100(122) for [Mo4S4(H2O)12]5+ to higher energy transitions at 522(660), 850(200) for [MoW3S4(H2O)12]5+. Oxidation of the 5+ cubes with for example [Fe(H2O)6]3+ gives first the 6+ cube which then decays with fragmentation to trinuclear products always with loss of W. While oxidation to the 6+ cube depends on reduction potentials, a different order is observed and other factors are important in the decay process.

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