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

Roffe, Gavin W and Cox, Hazel (2013) Computational study of the coordination of methane to first row transition metal dication complexes. Journal of Physical Chemistry, 117 (14). pp. 3017-3024. ISSN 0022-3654

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Abstract

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 ωB97XD hybrid functional and triple-ζ basis sets. The structure is dependent on the metal center; for the early transition metals η3 coordination is favored, whereas η2 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.

Item Type: Article
Schools and Departments: School of Life Sciences > Chemistry
Subjects: Q Science
Depositing User: Deeptima Massey
Date Deposited: 05 Jun 2013 13:30
Last Modified: 05 Jun 2013 13:30
URI: http://srodev.sussex.ac.uk/id/eprint/45274
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