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Synthesis, structure, and properties of molybdenum and tungsten cyano complexes with cuboidal M4(μ3-E)4 (M = Mo, W; E = S, Se, Te) cores

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

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Abstract

Four new tungsten and molybdenum cyano complexes of formula KCs5[W4S4(CN)12]·CH 3OH·2H2O (1), K6[W4Se4(CN)12]·6H 2O (2), K6[W4Te4(CN)12]·5H 2O (3), and K7[Mo4Te4(CN)12]·12H 2O (5) have been prepared by high-temperature 430-450 °C reaction of the polymeric chain compounds {W3S7Br4}x, {W3Se7Br4}x, {Mo3Te7I4}x and solid-state WTe2 with KCN, and crystallization from aqueous solutions. In addition Cs6[Mo4Te4(CN)12]·2H 2O (4) has been prepared by oxidation of 5 with bromine water. The molecular structures have been investigated by X-ray crystallography. Mixed-valence (3.5) compounds 1-4 are diamagnetic. Mixed-valence (3.25) compound 5 is paramagnetic (μ = 2.03 μB at 77 K). In addition to the structural data for these complexes IR and UV-vis spectroscopy have been used to characterize the complexes. Cyclic-voltammetry data have shown that M4E4n+ (M = Mo, W; E = S, Se, Te) cubes are capable of existing in three oxidation states ranging from the most oxidized (n = 6; 10 electrons) to the most reduced electron-precise (n = 4; 12 electrons). The 77Se, 125Te, and 183W NMR spectra of the cubes (1-3) demonstrate unambiguously the unaltered environments of the W and E atoms in aqueous solution. © 1999 American Chemical Society.

Publication metadata

Author(s): Fedin VP, Kalinina IV, Samsonenko DG, Mironov YV, Sokolov MN, Tkachev SV, Virovets AV, Podberezskaya NV, Elsegood MRJ, Clegg W, Sykes AG

Publication type: Article

Publication status: Published

Journal: Inorganic Chemistry

Year: 1999

Volume: 38

Issue: 9

Pages: 1956-1965

Print publication date: 03/04/1999

ISSN (print): 0020-1669

ISSN (electronic): 0974-746X

Publisher: American Chemical Society

URL: http://dx.doi.org/10.1021/ic980956z

DOI: 10.1021/ic980956z

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