Shanghai Key Laboratory of Molecular Catalysis and Innovative Material, Department of Chemistry, Fudan University, Shanghai, P. R. China
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Chem. Soc. Rev., 2014,43, 2799-2823
30 Sep 2013,
First published online
05 Feb 2014
Half-sandwich Cp*Ir and Cp*Rh metalacycles have been successfully applied in traditional domains encompassing organic transformations and catalysis in recent years, especially the catalytic activation of C–H bonds. Cyclometalation has proven to be a highly attractive and versatile synthetic method for the formation of organometallic metalacycles. This review intends to describe isolated and well-defined cyclometalated iridium/rhodium complexes that contain a Cp*M–C (M = Ir, Rh) bond stabilised by the intramolecular coordination of neutral donor atoms (N, C, O or P). The formation of metalamacrocycles and cages employing cyclometalated approaches is discussed. In focusing on selected mechanistic insights garnered from iridium/rhodium-catalysed functionalisation of C–H bonds involving cyclometalated complexes, a limited number of substrates will be discussed, but a broad range of mechanistic features is highlighted.
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