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The development of novel catalysts for C–H activation reactions with increased reactivity and improved selectivities has been attracting significant interest over the last two decades. More recently, promising results have been developed using tridentate pincer ligands, which form a stable C–M bond. Furthermore, based on mechanistic studies, the unique catalytic role of some metallacyclic intermediate species has been revealed. These experimental observations have subsequently translated into the rational design of advanced C–H activation catalysts in both Ru- and Ir-based systems. Recent breakthroughs in the field of C–H activation catalysed by metallacyclic intermediates are thus discussed.

Graphical abstract: Cyclometallated complexes as catalysts for C–H activation and functionalization

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