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