Issue 22, 2019

London dispersion effects in the coordination and activation of alkanes in σ-complexes: a local energy decomposition study

Abstract

Local energy decomposition (LED) analysis decomposes the interaction energy between two fragments calculated at the domain-based local pair natural orbital CCSD(T) (DLPNO-CCSD(T)) level of theory into a number of chemically meaningful contributions. Herein, this scheme is applied to the interaction between the transition metal (TM) and the alkane in σ-complexes. It is demonstrated that the often-neglected London dispersion (LD) energy is a fundamental component of the TM–alkane interaction for a wide range of experimentally characterized σ-complexes. LD effects determine the structure and the thermodynamic stability of σ-complexes and influence the selectivity of CH activation reactions. The magnitude of the LD energy can be modulated by increasing the size of the alkane and of the ancillary ligands on the TM. These results provide further evidence on the fundamental role that London dispersion plays in organometallic chemistry.

Graphical abstract: London dispersion effects in the coordination and activation of alkanes in σ-complexes: a local energy decomposition study

Supplementary files

Article information

Article type
Paper
Submitted
07 Mar 2019
Accepted
02 Apr 2019
First published
02 Apr 2019
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2019,21, 11569-11577

London dispersion effects in the coordination and activation of alkanes in σ-complexes: a local energy decomposition study

Q. Lu, F. Neese and G. Bistoni, Phys. Chem. Chem. Phys., 2019, 21, 11569 DOI: 10.1039/C9CP01309A

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