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Issue 10, 1998
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Unusual carbonyl and pentamethylcyclopentadienyl bonding modes in mixed rhodium–ruthenium clusters

Abstract

Thermolysis of [Ru3RhH2(CO)105-C5Me5)], 1, in hydrocarbon solvents affords the new pentanuclear cluster [Ru3Rh23-H)(µ2-CO)(µ3-CO)2(CO)6(µ-η15-CH2C5Me4)(η5-C5Me5)], 2, together with the known complex [Ru2Rh2(CO)85-C5Me5)2], 3. The reaction of 1 with Me3NO, in MeCN solution, followed by the immediate addition of one or two equivalents of PPh3 lead to the isolation of the mono– and di-phosphine substituted complexes [Ru3Rh(µ-H)242-CO)(µ2-CO)2(CO)6(PPh3)(η5-C5Me5)], 4, and [Ru3Rh(µ-H)242-CO)(µ2-CO)2(CO)5(PPh3)25-C5Me5)], 5, respectively. The new clusters have been characterised spectroscopically, and the structures of 2 and 5 established by single-crystal X-ray analyses. The metal framework in 2 is trigonal bipyramidal, with one C5Me5 ligand co-ordinated to a Rh atom in a terminal η5-bonding mode, the second cyclopentadienyl ligand has lost a methyl proton and the resultant –CH2 group is σ-bonded to one Ru atom while the C5Me4 ring is η5-bound to the adjacent Rh atom. The metal framework in 5 has opened out to give a butterfly arrangement with the Rh(η5-C5Me5) unit in one of the wing-tip positions. The butterfly is spanned by a novel µ42-bonded carbonyl ligand, and the two phosphines are terminally bound to two Ru atoms, one in a wing-tip site and the other in a hinge site.

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Article type: Paper
DOI: 10.1039/A803849J
New J. Chem., 1998,22, 1111-1117

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    Unusual carbonyl and pentamethylcyclopentadienyl bonding modes in mixed rhodium–ruthenium clusters

    W. Clegg, N. Feeder, S. Nahar, P. R. Raithby, G. P. Shields and S. J. Teat, New J. Chem., 1998, 22, 1111
    DOI: 10.1039/A803849J

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