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DOI: 10.1039/A805852K (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1998, 3825-3832

Triruthenium–iridium clusters containing alkyne ligands: synthesis, structure, and catalytic implications of [(µ-H)IrRu3(CO)11(µ3-η2-PhC[triple bond, length half m-dash]CPh)] and [IrRu3(CO)10(µ4-η2-PhC[triple bond, length half m-dash]CPh)(µ-η2-PhC[double bond, length half m-dash]CHPh)]

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Vincent Ferrand, Georg Süss-Fink, Antonia Neels and Helen Stoeckli-Evans

Abstract

The mixed-metal cluster [HIrRu3(CO)13] 1 reacts with one equivalent of disubstituted alkynes RC[triple bond, length half m-dash]CR to give [HIrRu3(CO)11(µ3-η2-RC[triple bond, length half m-dash]CR)] (R = Ph 2; R = Me 3), with a second equivalent of the alkyne the clusters [IrRu3(CO)10(µ4-η2-RC[triple bond, length half m-dash]CR)(µ-η2-RC[double bond, length half m-dash]CHR)] (R = Ph 4; R = Me 5) are obtained. The single-crystal X-ray structure analyses of 2 and 3 show these clusters to have a tetrahedral Ru3Ir framework containing the alkyne ligand coordinated in a parallel fashion over the Ru3 face of the metal skeleton. In contrast, the clusters 4 and 5 consist of a butterfly arrangement of the Ru3Ir framework with the alkyne ligand coordinated to all four metal atoms, giving an overall octahedral Ru3IrC2 skeleton, as demonstrated by the single-crystal structure analysis of 4. Cluster 1 is an excellent catalyst for the hydrogenation of diphenylacetylene to give stilbene (catalytic turnover number 990 within 15 min), clusters 2 and 4 are also catalytically active but seem to represent side-channels of the catalytic cycle.

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