Synthesis, characterisation and crystal structures of a series of pentanuclear arene-substituted clusters

Abstract
Reduction of the tetraosmium cluster [Os4H4(CO)12] with K–Ph2CO gave the cluster dianion [Os4H4(CO)11]2–1 in quantitative yield. This dianion was treated with [Ru(C6H6)(MeCN)3]2+ to give [RuOs4H46-C6H6)(CO)11]2 in fair yield, while the corresponding reaction with [Os(C6H6)(MeCN)3]2+ gave [Os5H46-C6H6)(CO)11]3 and [Os5H46-C6H6)(CO)12]4 in similar yields (ca. 25% each). Clusters 2–4 have been fully characterised by both spectroscopic and crystallographic methods. The crystal structures of 2 and 3 are isomorphous and both the molecules are isostrctural. Both contain a trigonal bipyramidal metal-core geometry with the η6-C6H6 co-ordinated to the Ru or Os atom in an equatorial position. Cluster 4 contains an Os4 tetrahedron with one Os–Os edge bridged by an ‘Os(η6-C6H6)(CO)’ unit. Complex 3 is not convertible into 4 under thermolytic and photolytic conditions in the presence of CO, or 4 into 3 in the absence of CO.

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