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)]

• 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-T ePh)(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.

Ämnesord

NATURVETENSKAP  -- Fysik -- Atom- och molekylfysik och optik (hsv//swe)

NATURAL SCIENCES  -- Physical Sciences -- Atom and Molecular Physics and Optics (hsv//eng)

Nyckelord

Triruthenium

Carbonyls

Furyne cluster

Carbene

Diphenyl ditelluride

Unsymmetrical alkyne binding

Oxidative-addition

X-ray structures

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