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Formation of Agostic Structures Driven by London Dispersion
Author(s) -
Lu Qing,
Neese Frank,
Bistoni Giovanni
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201801531
Subject(s) - agostic interaction , dispersion (optics) , cluster (spacecraft) , chemistry , chemical physics , metal , physics , organic chemistry , computer science , optics , programming language
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.