Investigations into CÀ 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 CÀ 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 CÀ 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.

Despite their synthetic utility, practical and reliable methods to prepare diversely functionalized aromatic acyl silanes (benzoyl silanes) remain scarce. We herein report that cobalt complexes are able to successfully engage...

Investigations into C-H amidation reactions using electron-deficient cationic half-sandwich d6 metal complexes revealed that the indenyl-derived catalyst [Ind*RhCl2]2 significantly accelerated the directed ortho C-H amidation of benzoyl silanes using 1,4,2-dioxazol-5-ones. Ring slippage involving a haptotropic 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.

Investigations into C−H amidation reactions catalysed by cationic half‐sandwich d6 metal complexes revealed that the indenyl‐derived catalyst [Ind*RhCl2]2 significantly accelerated the directed ortho C−H amidation of benzoyl silanes using 1,4,2‐dioxazol‐5‐ones. Ring slippage involving a haptotropic η5 to η3 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.