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Pure Appl. Chem., 2003, Vol. 75, No. 4, pp. 435-443

http://dx.doi.org/10.1351/pac200375040435

Carbenes. Pincers, chelates, and abnormal binding modes

R. H. Crabtree

225 Prospect St, New Haven, CT 06520-8107, USA

Abstract: Routes to pincer and chelate carbene complexes of Pd, Rh, and Ir include double geminal CH activation, metallation, and CH activation. Abnormal binding via imidazole C5 can occur, and ion pairing can strongly influence C2 vs. C5 binding. Prior ligand binding via pyridine N before metallation is not essential. Computational methods are used extensively, for example, to compare N vs. C binding in imidazole. The possibility of C binding by histidine in metalloenzymes is discussed.