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 η 5-interaction from the five-membered ring, both of the indenyl ligand. The X-ray crystal structure determination of Ru3(μ 3-PPhCH2PPh2)(μ 3-C9H5Ph2)(CO)5 (4) is reported. A related reaction was found between Ru3(μ-H)(μ-CCCPh2)(μ-OH)(CO)9 and Co2(CO)8, which afforded CoRu3(μ 3-C9H6Ph) (μ-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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Bruce, M.I., Skelton, B.W., White, A.H. et al. Cyclisation of Allenylidene Ligands to Indenyl Groups on Ruthenium Clusters. Journal of Cluster Science 13, 235–247 (2002). https://doi.org/10.1023/A:1015552103043
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DOI: https://doi.org/10.1023/A:1015552103043