Contrasting Electronic Requirements for C-H Binding and C-H Activation in d(6) Half-Sandwich Complexes of Rhenium and Tungsten

Thenraj, Murugesan and Samuelson, Ashoka G (2015) Contrasting Electronic Requirements for C-H Binding and C-H Activation in d(6) Half-Sandwich Complexes of Rhenium and Tungsten. In: JOURNAL OF COMPUTATIONAL CHEMISTRY, 36 (24). pp. 1818-1830.

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Abstract

A computational study of the interaction half-sandwich metal fragments (metal=Re/W, electron count=d(6)), containing linear nitrosyl (NO+), carbon monoxide (CO), trifluorophosphine (PF3), N-heterocyclic carbene (NHC) ligands with alkanes are conducted using density functional theory employing the hybrid meta-GGA functional (M06). Electron deficiency on the metal increases with the ligand in the order NHC < CO < PF3 < NO+. Electron-withdrawing ligands like NO+ lead to more stable alkane complexes than NHC, a strong electron donor. Energy decomposition analysis shows that stabilization is due to orbital interaction involving charge transfer from the alkane to the metal. Reactivity and dynamics of the alkane fragment are facilitated by electron donors on the metal. These results match most of the experimental results known for CO and PF3 complexes. The study suggests activation of alkane in metal complexes to be facile with strong donor ligands like NHC. (C) 2015 Wiley Periodicals, Inc.

Item Type:	Journal Article
Publication:	JOURNAL OF COMPUTATIONAL CHEMISTRY
Publisher:	WILEY-BLACKWELL
Additional Information:	Copy right for this article belongs to the WILEY-BLACKWELL, 111 RIVER ST, HOBOKEN 07030-5774, NJ USA
Keywords:	d(6)-half-sandwich complexes; C-H activation; ligand effects; alkane chain walking; density functional theory study
Department/Centre:	Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited:	11 Sep 2015 04:10
Last Modified:	11 Sep 2015 04:10
URI:	http://eprints.iisc.ac.in/id/eprint/52309

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