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Issue 19, 1992
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Synthesis and molecular structures of some novel anionic diselenides

Abstract

The anions [Se(S)C[double bond, length half m-dash]C(CN)2]2–(imnts) and [Se2C[double bond, length half m-dash]C(CN)2]2–(imns) undergo oxidative dimerization reactions which have been studied by cyclic voltammetry. They proceed via a one-electron oxidation followed by a rapid chemical radical dimerization (ECirr mechanism) with Eimnts=–0.2 V and Eimns=–0.3 V versus SCE. The resulting anionic diselenides have been characterized by X-ray structure analysis of [NBu4]2[{(NC)2C[double bond, length half m-dash]C(S)Se–}2]1, [AsPh4]2[{(NC)2C[double bond, length half m-dash]C(S)Se–}2]2 and [AsPh4]2[{(NC)2C[double bond, length half m-dash]C(Se)Se–}2]3. The anions in 13 all exhibit a trans arrangement with an inversion centre bisecting the Se–Se bridges. The average Se–Se bond length is 2.330 Å. There are two types of bonds involving sp2-hybridized carbon and different chalcogen atoms. The average Se–C bond distance involving selenium of the diselenide group is 1.936 Å and corresponds to a single bond. The chalcogen–carbon bonds involving anionic sulfur atoms of 1 and 2 as well as Se of 3 are 1.668, 1.669 and 1.81 Å respectively and seem indicative of some double-bond character with charge delocalization over the dimeric dianions.

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Article type: Paper
DOI: 10.1039/DT9920002781
Citation: J. Chem. Soc., Dalton Trans., 1992,0, 2781-2785
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    Synthesis and molecular structures of some novel anionic diselenides

    H. Hummel, T. Fischer, D. Gruss, A. Franke and W. Dietzsch, J. Chem. Soc., Dalton Trans., 1992, 0, 2781
    DOI: 10.1039/DT9920002781

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