IrIJIII) metallacycles were applied as catalysts for the hydrosilylation of various ketimines and aldimines with sodium tetrakisij(3,5-trifluoromethyl)phenyl]borate, NaBArF 24 , as an additive. By using a slight excess of the organosilane reagent, the reactions proceeded rapidly and efficiently, at low catalyst loadings and at room temperature. Several examples of cationic IrIJIII) catalysts could be synthesised, characterized and tested.In situ-generated catalysts proved to be more active as compared to isolated ones and species with non-coordinating BArF 24 counterion gave the highest catalytic activities.
Pentamethylcyclopentadienyl cyclometallated complexes have been used to catalyse a variety of organic transformations over the last decades. However, the huge potential of pentamethylcyclopentadienyl iridacycles has only been truly recognised in recent years. Indeed, an upsurge of reports on such new half‐sandwich iridium(III) metallacycles has been observed. The application of these organometallic complexes in various homogeneous catalysed organic reactions has led to the development of environmentally and economically beneficial routes towards important and highly functionalised fine chemicals. Studied reactions include hydrogenation, amine alkylation, dehydrogenation, oxidation and hydrofunctionalisation reactions as well as dynamic kinetic resolutions (DKR). This minireview focusses specifically on the recent applications of half‐sandwich iridium(III) metallacycles in such processes.
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