Cyclisation of allenylidene ligands to indenyl groups on ruthenium clusters
Date
2002
Authors
Bruce, M.
White, A.
Skelton, B.
Zaitseva, N.
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Journal article
Citation
Journal of Cluster Science, 2002; 13(2):235-247
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Michael I. Bruce, Brian W. Skelton, Allan H. White and Natasha N. Zaitseva
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Abstract
Thermolysis of Ru<inf>3</inf> cluster complexes containing diarylallenylidene and dppm ligands results in phenyl migration from dppm to the allenylidene with concomitant H migration and C-C bond formation reactions to give several complexes each containing a cluster-bound indenyl group. In initially-formed complexes 3 or 6, the diarylindenyl group is attached to the cluster by two localized C=C double bonds of one aryl group and a benzylic interaction of the remaining C=C double bond combined with one carbon of the five-membered ring. Thermal rearrangement of these complexes with concomitant loss of CO gives 4 or 7, respectively, in which the indenyl group is more symmetrically bonded to the cluster by two C=C double bonds from the six-membered ring and an η<sup>5</sup>-interaction from the five-membered ring, both of the indenyl ligand. The X-ray crystal structure determination of Ru<inf>3</inf>(μ<inf>3</inf>-PPhCH<inf>2</inf>PPh<inf>2</inf>)(μ <inf>3</inf>-C<inf>9</inf>H<inf>5</inf>Ph<inf>2</inf>)(CO)<inf>5</inf> (4) is reported. A related reaction was found between Ru<inf>3</inf>(μ-H)(μ -CCCPh<inf>2</inf>)(μ-OH)(CO)<inf>9</inf> and Co<inf>2</inf>(CO) <inf>8</inf>, which afforded CoRu<inf>3</inf> (μ<inf>3</inf>-C <inf>9</inf>H<inf>6</inf>Ph) (μ-CO)<inf>4</inf>(CO)<inf>5</inf> (8), also structurally characterized, in which the indenyl group caps the Ru<inf>3</inf> face of a CoRu<inf>3</inf> tetrahedron; unusually, there are four CO groups bridging the three Co-Ru bonds.
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The original publication is available at www.springerlink.com