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DOI: 10.1039/A607930J (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 1747-1752

Preparation, structure and properties of trinuclear [M3Se4(CN)9]5- (M = Mo or W) complexes obtained from M3Se7 core compounds and related studies

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Vladimir P. Fedin, Gert J. Lamprecht, Takamitsu Kohzuma, William Clegg, Mark R. J. Elsegood and A. Geoffrey Sykes

Abstract

The preparations of [Mo3Se4(CN)9]5- and [W3Se4(CN)9]5- by reacting polymeric {M3Se7Br4}x or the derivative [M3Se7Br6]2- ions (M = Mo or W) with CN- are described. Both products were isolated as the Cs5[M3Se4(CN)9]· CsCl·4H2O salts. The crystal structures are essentially the same with corresponding cell dimensions within 0.3% of each other, and those for the W compound slightly the larger. The M3Se4 cores (approximate symmetry C3v) can be described as distorted incomplete cubes with, in the tungsten case, dave(W–W) 2.829, dave(W–µ-Se) 2.449, dave(W–µ3-Se) 2.497, dave(W–C) 2.179 and dave(C–N) 1.16 Å. A different feature as compared to the sulfide analogues is the weak dimerisation of two trimer units giving short Se · · · Se contacts (≈3.5 Å). The UV/VIS spectra of brown [Mo3Se4(CN)9]5- and green [W3Se4(CN)9]5- indicate a red shift on replacing Mo by W, and a similar shift on exchanging S for Se. In electrochemical studies using cyclic, square-wave and differential pulse voltammetric techniques reduction potentials for the [M3Se4(CN)9]5-/6- couple (vs. normal hydrogen electrode) of -0.63 (Mo) and -0.97 V (W) were obtained. Using a Hg–Au electrode two additional reduction steps were observed, and there is evidence for the formation of Hg-containing heterometallic clusters. Properties of the two aqua ions [M3Se7(H2O)6]4+ were also studied, where these are similarly converted to [M3Se4(CN)9]5- by Se-abstraction and substitution of H2O by CN-.

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