The Indenyl Effect: Accelerated C−H Amidation of Arenes via Ind*Rh ^III Nitrene Transfer Catalysis**

Abstract

Abstract Investigations into C−H amidation reactions catalysed by cationic half‐sandwich d 6 metal complexes revealed that the indenyl‐derived catalyst [Ind*RhCl 2 ] 2 significantly accelerated the directed ortho C−H amidation of benzoyl silanes using 1,4,2‐dioxazol‐5‐ones. Ring slippage involving a haptotropic η 5 to η 3 rearrangement of the indenyl complex proposedly enables ligand substitution at the metal centre to proceed via associative, rather than dissociative pathways, leading to significant rate and yield enhancements. Intriguingly, this phenomenon appears specific for C−H amidation reactions involving weakly coordinating carbonyl‐based directing groups with no acceleration observed for the corresponding reactions involving strongly coordinating nitrogen‐based directing groups.