The hydrosilylation of terminal alkynes is catalyzed by [Cp*IrCl2]2 to afford selectively the β-(Z)-vinylsilanes in high yields. A catalytic cycle based on an Ir(III)−Ir(V) redox process is proposed.

Reaction of the dimeric species [Cp*IrCl2]2 with a number of organic substrates carrying a terminal alkyne functionality (RCCH) in the presence of water leads to C⋮C bond cleavage to form Cp*IrCl(CH2R)(CO). The reaction pathway has been studied both experimentally and computationally.

The reaction of a terminal alkyne (RCCH) and an aniline (R 0 C 6 H 4 NH 2 ) with the dinuclear species [Cp*IrCl 2 ] 2 afforded cyclometalated amino-carbene derivatives Cp*Ir(Cl)[dC(CH 2 R)NHC 6 H 3 R 0 ] via a hydroamination and an orthometalation. The reaction pathway has been examined through deuterium labeling and computational studies.

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The reductive homocoupling of 9-bromofluorene is catalyzed by 0.1 mol % Ru 3 (CO) 12 in refluxing xylene, with a TON in excess of 3000. A stoichiometric reaction affords the novel cluster Ru 4 (µ 3 -OMe)-(µ 3 -OH)(µ-Br) 2 (CO) 10 , which is found to be even more catalytically active. Further reaction of this cluster with bromofluorene gives another novel cluster, Ru 4 (µ 4 -O)(µ-Br) 6 (CO) 8 , which is inactive. atoms, followed by difference maps for the light, non-hydrogen atoms. All non-hydrogen atoms were generally given anisotropic displacement parameters in the final model (except for 5 below). Cluster 2 exhibited disorder of two carbonyls on Ru(4) and one carbonyl on Ru(5). These were each modeled with two alternative sites of equal occupancies, and appropriate restraints on their anisotropic parameters and bond distances were placed.Cluster 5 contained three molecules in the asymmetric unit. It was refined as a racemic twin. The data quality was poor, and there appeared to be disorder in molecule A, which was not modeled.All the carbon atoms were given isotropic thermal parameters, as well as the µ 4 -O atom in molecule A.