Cyclometalative C–H bond activation in rare earth and actinide metal complexes

Cyclometalative C–H bond activation is a process that is commonly encountered in the field of organometallic chemistry. In rare earth and actinide complexes, ligand cyclometalation is most prevalent in highly reactive alkyl and hydrido species. Numerous factors promote ligand cyclometalation and influence the rate at which it occurs. This tutorial review discusses key issues relevant to ligand cyclometalation in rare earth and actinide complexes, including kinetic and mechanistic considerations. A variety of examples is presented for a wide range of ligand types and metals, the scope of which is intended to include routine cases, while also highlighting exceptional cyclometalation reactions that lead to unusual bonding modes. The reaction chemistry of cyclometalated rare earth and actinide complexes with various small molecule substrates (e.g. phenol, anilines, triethylammonium salts, alkynes, olefins, hydrogen and hydrocarbons) is also outlined.