Cyclisation of Allenylidene Ligands to Indenyl Groups on Ruthenium Clusters |
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Authors: | Michael I Bruce Brian W Skelton Allan H White Natasha N Zaitseva |
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Institution: | (1) Department of Chemistry, Adelaide University, Adelaide, South Australia, 5005, Australia;(2) Department of Chemistry, University of Western Australia, Crawley, Western Australia, 6009, Australia |
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Abstract: | Thermolysis of Ru3 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
5-interaction from the five-membered ring, both of the indenyl ligand. The X-ray crystal structure determination of Ru3(
3-PPhCH2PPh2)(
3-C9H5Ph2)(CO)5 (4) is reported. A related reaction was found between Ru3(-H)(-CCCPh2)(-OH)(CO)9 and Co2(CO)8, which afforded CoRu3(
3-C9H6Ph) (-CO)4(CO)5 (8), also structurally characterized, in which the indenyl group caps the Ru3 face of a CoRu3 tetrahedron; unusually, there are four CO groups bridging the three Co–Ru bonds. |
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Keywords: | allenylidene cobalt cyclisation indene ruthenium |
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