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Use of the Cationic Fragments [Ru(η5-C5H5) (MeCN)3]+ and [M(η6-C6H5R)(MeCN)3]+ (M=Os, Ru; R=H, Me) as Ionic Coupling Reagents in the Synthesis of the Clusters [Os4M2(CO)12(η6-C6H5R)], [Os4M(CO)12(η6-C6H6)(Au2dppm)] and [Os5Ru(CO)15(η5-C5H5)(AuPPh3)]*

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Abstract

The clusters [H2Os4M(CO)12eta6-C6H6)] (M=Os, Ru) may be deprotonated to generate anions [Os4M(CO)12eta6-C6H6)]2- which react with [M′eta6-C6H5R) (MeCN)3]2+(M′=Os, Ru; R=H, Me) to give the bicapped tetrahedral clusters [Os4(CO)12MM′eta6-C6H5R)2]. Whereas [Os4(CO)12M2eta6-C6H6)2] (M=Os, Ru) have one Meta6-C6H6) unit in a site connected to three other metals, {3}, and one in a site connected to four other metals, {4}, [Os4(CO)12OsRueta6-C6H6)2] has the Rueta6-C6H6) unit in the {3} site irrespective of whether the Os or Ru anion is capped. Coupling of these anions with Au2dppm yields [Os4M(CO)12eta6-C6H6)(Au2dppm)] (M=Os, Ru), which have the arene ligand in the axial site of a trigonal bipyramid and the digold unit capping two faces. Reduction of [H2Os5(CO)15] with K/Ph2CO and coupling with [Rueta5-C5H5)(MeCN)3]2+yields the monoanion [Os5(CO)15Rueta5-C5H5)]− which reacts with [AuPPh3]+ generating [Os5(CO)15Rueta5-C5H5)(AuPPh3)] with the “Ru(C5H5)” unit in the terminal {3} site.

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Authors and Affiliations

  1. Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, UK

    Muna R. A. Al-Mandhary, Radchada Buntem, Andrew J. Edwards, John F. Gallagher, Jack Lewis, Chi-Keung Li, M. Carmen Ramirez de Arellano & Gregory P. Shields

  2. Department of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY, UK

    Cheryl L. Doherty & Paul R. Raithby

  3. CCLRC Daresbury Laboratory, Daresbury, Warrington, WA4 4AD, UK

    Paul R. Raithby

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  1. Muna R. A. Al-Mandhary
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  2. Radchada Buntem
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Correspondence to Paul R. Raithby.

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*Dedicated to Professor F. A. Cotton in recognition of his continuing contributions to inorganic chemistry.

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Al-Mandhary, M.R.A., Buntem, R., Doherty, C.L. et al. Use of the Cationic Fragments [Ru(η5-C5H5) (MeCN)3]+ and [M(η6-C6H5R)(MeCN)3]+ (M=Os, Ru; R=H, Me) as Ionic Coupling Reagents in the Synthesis of the Clusters [Os4M2(CO)12(η6-C6H5R)], [Os4M(CO)12(η6-C6H6)(Au2dppm)] and [Os5Ru(CO)15(η5-C5H5)(AuPPh3)]*. J Clust Sci 16, 127–150 (2005). https://doi.org/10.1007/s10876-005-4402-2

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  • DOI: https://doi.org/10.1007/s10876-005-4402-2

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