Formation of Agostic Structures Driven by London Dispersion
Dr. Qing Lu
Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, Germany
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Prof. Dr. Frank Neese
Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, Germany
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Dr. Giovanni Bistoni
Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, Germany
Search for more papers by this authorDr. Qing Lu
Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, Germany
Search for more papers by this authorCorresponding Author
Prof. Dr. Frank Neese
Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, Germany
Search for more papers by this authorCorresponding Author
Dr. Giovanni Bistoni
Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, Germany
Search for more papers by this authorGraphical Abstract
The importance of dispersion: DLPNO-CCSD(T) local energy decomposition analysis was used to elucidate the nature of β-agostic interactions. Short-range London dispersion between the agostic C−H bond and the metal center drives the formation of agostic structures to a large extent. These results were used to rationalize a series of previously published experimental findings.
Abstract
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.
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