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Computational study of the coordination of methane to first row transition metal dication complexes

journal contribution
posted on 2023-06-08, 15:10 authored by Gavin W Roffe, Hazel CoxHazel Cox
The coordination of methane, the first step in methane activation, to coordinately unsaturated first row transition metal dication complexes has been studied computationally to determine the most stable metal-methane interaction. The geometries and the vibrational frequencies of the encounter complexes [M(pyridine)2(CH4)]2+ have been determined using density functional theory with the ?B97XD hybrid functional and triple-? basis sets. The structure is dependent on the metal center; for the early transition metals ?3 coordination is favored, whereas ?2 is more favorable for the later transition metals. The periodic trend in methane binding energies in the [M(pyridine)2(CH4)]2+ complexes follows the trend in electron affinity until the Mn complex but then exhibits decreasing energies from Fe to Zn. This is attributed to increasing Pauli repulsion and ligand–ligand repulsion. For the most stable complex, [Cr(pyridine)2(CH4)]2+, the structures, energies, and spin states of the key intermediates and products in the oxidative addition/reductive elimination pathway have been investigated. It is found that the reaction is thermodynamically favorable and indicates that two-state reactivity may play an important role in lowering the energy of the hydridomethyl intermediate.

History

Publication status

  • Published

Journal

Journal of Physical Chemistry

ISSN

0022-3654

Publisher

American Chemical Society

Issue

14

Volume

117

Page range

3017-3024

Department affiliated with

  • Chemistry Publications

Full text available

  • No

Peer reviewed?

  • Yes

Legacy Posted Date

2013-06-05

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