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Issue 12, 1990
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Reductive cleavage of the C–S bond in [Ni2(cp)2(µ-SR)2](cp =η-C5H5) by LiAlH4. Crystal structures of [Ni2(cp)2(µ-SPh)2] and [Ni2(cp)2{µ-o-(SCH2)2- C6H4}]

Ngan-Fong Ho,  Thomas C. W. Mak  and  Tien-Yau Luh 

Abstract

The first example of the reductive cleavage of the carbon–sulphur bond in organonickel thiolato complexes [Ni2(cp)2(SR)2](cp =η-C5H5) by LiAlH4 is reported. Preliminary mechanistic studies suggest that some kind of hydridic species may play an important role in the reduction. Electrochemical investigation of the bridged thiolatonickel complexes indicates that they undergo reversible one-electron reduction without cleavage of the C–S bond. The molecular structures of [Ni2(cp)2(SPh)2](1a) and [Ni2(cp)2{o-(SCH2)2C6H4](1e) have been determined by X-ray crystallography. The crystal data are: (1a), space group Pbca, a= 8.043(3), b= 12.774(3), c= 19.610(5)Å, Z= 4, R= 0.043 for 1 867 observed reflections; (1e), space group P21/a, a= 10.348(3), b= 10.880(3), c= 14.785(4)Å, β= 97.78(2)°, Z= 4, R= 0.046 for 1 772 observed reflections.

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Article type: Paper
DOI: 10.1039/DT9900003591
Citation: J. Chem. Soc., Dalton Trans., 1990,0, 3591-3595
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    Reductive cleavage of the C–S bond in [Ni2(cp)2(µ-SR)2](cp =η-C5H5) by LiAlH4. Crystal structures of [Ni2(cp)2(µ-SPh)2] and [Ni2(cp)2{µ-o-(SCH2)2- C6H4}]

    N. Ho, T. C. W. Mak and T. Luh, J. Chem. Soc., Dalton Trans., 1990, 0, 3591
    DOI: 10.1039/DT9900003591

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