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    Some ruthenium complexes containing cyanocarbon ligands: syntheses, structures and extent of electronic communication in binuclear systems

    Access Status
    Fulltext not available
    Authors
    Bruce, M.
    Buntine, Mark
    Costuas, K.
    Ellis, B.
    Halet, J.
    Low, P.
    Skelton, B.
    White, A.
    Date
    2004
    Type
    Journal Article
    
    Metadata
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    Citation
    Bruce, Michael I. and Buntine, Mark A. and Costuas, Karine and Ellis, Benjamin G. and Halet, Jean-Francois and Low, Paul J. and Skelton, Brian W. and White, Allan H. 2004. Some ruthenium complexes containing cyanocarbon ligands: Syntheses, structures and extent of electronic communication in binuclear systems. Journal of Organometallic Chemistry 689 (21): pp. 3308-3326.
    Source Title
    Journal of Organometallic Chemistry
    DOI
    10.1016/j.jorganchem.2004.07.030
    ISSN
    0022328X
    URI
    http://hdl.handle.net/20.500.11937/29715
    Collection
    • Curtin Research Publications
    Abstract

    The preparation of several ruthenium complexes containing cyanocarbon anions is reported. Deprotonation (KOBut) of [Ru(NCCH2CN)(PPh3)2Cp]PF6 (1) gives Ru{N=C=CH(CN)}(PPh3)2Cp (2), which adds a second [Ru(PPh3)2Cp]+ unit to give [{Ru(PPh3)2Cp}2(μ-NCCHCN)]+ (3). Attempted deprotonation of the latter to give the μ-NCCCN complex was unsuccessful. Similar chemistry with tricyanomethanide anion gives Ru{N=C=C(CN)2}(PPh3)2Cp (4) and [{Ru(PPh3)2Cp}2{μ-NCC(CN)CN}]PF6 (5), and with pentacyanopropenide, Ru{N=C=C(CN)C(CN)C(CN)2}(PPh3)2Cp (6) and [{Ru(PPh3)2Cp}2{μ-NCC(CN)C(CN)C(CN)CN}]PF6 (7). The Ru(dppe)Cp* analogues of 6 and 7 (8 and 9) were also prepared. Thermolysis of 6 (refluxing toluene, 12 h) results in loss of PPh3 and formation of the binuclear cyclic complex {Ru(PPh3)Cp[μ-N=C={C(CN)=C(CN)2}CN]}2 (10). The solid-state structures of 2–4 and 8–10 have been determined and the nature of the isomers shown to be present in solutions of the binuclear cations 7 and 9 by NMR studies has been probed using Hartree–Fock and density functional theory.

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