Contrasting electronic requirements for C-H binding and C-H activation in d(6) half-sandwich complexes of rhenium and tungsten

• Published in: Journal of computational chemistry 2015-09, Vol.36 (24), p.1818-1830
• Main Authors: Thenraj, Murugesan, Samuelson, Ashoka G
• Format: Article
• Language: English
• ISSN: 1096-987X
• DOI: 10.1002/jcc.24002

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.