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Issue 4, 2001
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Reactions of nickelocene with an Ru5 cluster: crystal structures of two nickel–ruthenium clusters containing C2 ligands

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Abstract

Reactions of nickelocene with Ru55-C2)(μ-SMe)2(μ-PPh2)2(CO)11 have given NiRu56-C2)(μ-SMe)2(μ-PPh2)2(CO)9Cp2 and Ni2Ru46-C2)(μ-SMe)2(μ-PPh2)2(CO)8Cp2 whose molecular structures have been determined. The NiRu5 cluster is related to other heterometallic clusters containing FeRu5, Ru6 or Co2Ru5 cores which contain two edge-fused squares supporting the C2 ligand, one carbon occupying the centre of each square face while retaining the C–C bond. However, there is no formal M–M interaction along the shared edge. Substitution of CO groups by Cp on one Ru atom has occurred. The structure of the Ni2Ru4 cluster is similar, with the six-membered ring having the boat conformation. The C2 ligand takes up two disordered (1  1) positions, either parallel or perpendicular to the non-bonding Ni  Ni vector. Extended Hückel and density functional calculations have been carried out on Ni2Ru46-C2)(μ-SMe)2(μ-PPh2)2(CO)8Cp2 to rationalise these two observed coordination modes of the C2 unit to the metal framework. Results suggest that the two arrangements are isoenergetic and that the M–C bonding follows the Dewar–Chatt–Duncanson model as previously found for related C2-containing polynuclear organometallic clusters.

Graphical abstract: Reactions of nickelocene with an Ru5 cluster: crystal structures of two nickel–ruthenium clusters containing C2 ligands

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Publication details

The article was received on 29 Jun 2000, accepted on 07 Dec 2000 and first published on 31 Jan 2001


Article type: Paper
DOI: 10.1039/B005210H
Citation: J. Chem. Soc., Dalton Trans., 2001, 414-422
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    Reactions of nickelocene with an Ru5 cluster: crystal structures of two nickel–ruthenium clusters containing C2 ligands

    C. J. Adams, M. I. Bruce, J. Halet, S. Kahlal, B. W. Skelton and A. H. White, J. Chem. Soc., Dalton Trans., 2001, 414
    DOI: 10.1039/B005210H

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