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Routes to Higher Nuclearity Mixed-Metal Carbonyl Clusters Using the [Rh(η5-C5Me5)(NCMe)3]2+ Dication as a Building Block

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Abstract

Reaction of the [Rh(η5-C5Me5)(NCMe)3]2+ (1) dication with the hexaosmium [Os6(CO)17]2− (2) dianion leads to the initial formation of [Os6(CO)17Rh(η5-C5Me5)] (3). This cluster readily adds CO to form [Os6(CO)18Rh(η5-C5Me5)] (4) which has been characterised crystallographically. 3 also adds dihydrogen to give [Os6H2(CO)17Rh(η5-C5Me5)] (5) and undergoes a substitution reaction with PPh3 to form [Os6(CO)16(PPh3)Rh(η5-C5Me5)] (6). With the [Ru6(CO)18]2− (7) dianion, [Rh(η5-C5Me5)(NCMe)3]2+ (1) reacts to form three mixed-metal clusters [Ru5(CO)15Rh(η5-C5Me5)] (8), [Ru6(CO)18Rh(η5-C5Me5)] (9) and [Ru6(CO)18Rh25-C5Me5)2] (10). The clusters have been characterised spectroscopically and the structures of 8 and 10 have been confirmed crystallographically. The cluster 8 undergoes a substitution reaction with P(OMe)3 to form the disubstituted product [Ru5(CO)13(P(OMe)3)2Rh((η5-C5Me5)] (11) which has also been characterised crystallographically.

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Acknowledgments

We gratefully acknowledge the support of the Cambridge Commonwealth Trust and the United Kingdom Committee of Vice Chancellors and Principals (to S. N.) and the Cambridge Crystallographic Data Centre (to G. P. S.). We are also grateful to the EPSRC for a Senior Fellowship (to P. R. R.).

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Correspondence to Paul R. Raithby.

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This paper is dedicated to Professor Malcolm H. Chisholm FRS in recognition of his many seminal contributions to chemistry.

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Nahar, S., Davies, J.E., Shields, G.P. et al. Routes to Higher Nuclearity Mixed-Metal Carbonyl Clusters Using the [Rh(η5-C5Me5)(NCMe)3]2+ Dication as a Building Block. J Clust Sci 21, 379–396 (2010). https://doi.org/10.1007/s10876-010-0331-9

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