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Publication Detail
Unsymmetrical alkyne binding to a triruthenium centre: Oxidative-addition of diphenyl ditelluride to the furyne cluster [Ru-3(CO)(7)(mu-H)(mu(3)-eta(2)-C4H2O){mu-P(C4H3O)(2)}(mu-dppm)]
  • Publication Type:
    Journal article
  • Publication Sub Type:
    Article
  • Authors:
    Ghosh S, Hogarth G, Kabir SE, Nordlander E, Salassa L, Tocher DA
  • Publisher:
    ELSEVIER SCIENCE SA
  • Publication date:
    15/05/2011
  • Pagination:
    1982, 1989
  • Journal:
    J ORGANOMET CHEM
  • Volume:
    696
  • Issue:
    10
  • Print ISSN:
    0022-328X
  • Language:
    EN
  • Keywords:
    Triruthenium, Carbonyls, Furyne cluster, Carbene, Diphenyl ditelluride, Unsymmetrical alkyne binding, Oxidative-addition, X-ray structures, X-RAY STRUCTURES, CARBONYL CLUSTERS, BRIDGING DPPM, COMPLEXES, LIGANDS, REACTIVITY, ISOMERIZATION, CARBENE, DENSITY
  • Addresses:
    Hogarth, G
    UCL
    Dept Chem
    London
    WC1H OAJ
    England
Abstract
Oxidative-addition of PhTe2Ph to the furyne cluster [Ru-3(CO)(7)(mu-H)(mu(3)-eta(2)-C4H2O){mu-P(C4H3O)(2)}(mu-dppm)] (1) results in the isolation of four complexes; (i) the previously reported 54-electron cluster [Ru-3(CO)(6)(mu(3)-Te)(2)(mu-TePh)(2)(mu-dppm)] (5) which results from elimination of trifuryl phosphine, (ii) the furenyl cluster [Ru-3(CO)(5)(mu-eta(2)-C4H3O){mu-P(C4H3O)(2)}(mu-TePh)(2)(mu-dppm)] (6) which results from carbon-hydrogen bond formation and (iii) two new 50-electron complexes [Ru-3(CO)(5)(mu-H)(mu(3)-eta(2)-C4H2O){mu-P(C4H3O)(2)}(mu-TePh)(2)(kappa(2)-dppm)] (7) and [Ru-3(CO)(4)(mu-H){P(C4H3O)(3)}(mu(3)-eta(2)-C4H2O){mu-P(C4H3O)(2)}(mu-TePh)(2)(kappa(2)-dppm)] (8) both containing unsymmetrical furyne ligands. The structures of all the new compounds have been unambiguously established by single crystal X-ray crystallography. Further reactivity studies have provided a clear understanding of the relative sequence of the key oxidative-addition and reductive-elimination processes, showing that 6 is an intermediate in the formation of 7. DFT calculations have been used to shed light on the unsymmetrical binding of the furyne ligand in 7 and also to show that the adopted position of the heteroatom within the furyne ring can vary within complexes of this type. (C) 2010 Elsevier B.V. All rights reserved.
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