Formation of Agostic Structures Driven by London Dispersion

Agostic interactions between a C−H bond and a transition metal are commonly crucial in catalytic polymerization processes. Herein, a quantitative study of the nature of β‐agostic interactions in a series of systems of importance in C−H bond activation reactions is reported. The analysis, characterized by the use of a coupled‐cluster‐based energy decomposition scheme, demonstrates that short‐range London dispersion between the agostic C−H bond and the metal center plays a fundamental role in affecting the structural stability of these systems, contrary to a widely held view. These results are used to rationalize a series of previously published experimental findings.