Methane C–H Activation via 3d Metal Methoxide Complexes with Potentially Redox-Noninnocent Pincer Ligands: A Density Functional Theory Study

This paper reports a density functional theory study of 3d transition-metal methoxide complexes with potentially redox-noninnocent pincer supporting ligands for methane C–H bond activation to form methanol (L n M-OMe + CH 4 → L n M–Me + CH 3 OH). The three types of tridentate pincer ligands [terpyridine (NNN), bis(2-pyridyl)phenyl- C, N, N ′ (NCN), and 2,6-bis(2-phenyl)pyridine- N, C, C ′ (CNC)] and different first-row transition metals (M = Ti, V, Cr, Mn, Fe, Co, Ni, and Cu) are used to elucidate the reaction mechanism as well as the effect of the metal identity on the thermodynamics and kinetics of a methane activation reaction. Spin-density analysis indicates that some of these systems, the NNN and NCN ligands, have redox-noninnocent character. A four-centered, kite-shaped transition state, σ-bond metathesis, or oxidative hydrogen migration has been found for methane activation for the complexes studied. Calculations suggest that the d electron count is a more significant factor than the metal formal charge in controlling the thermodynamics and kinetics of C–H activation and late 3d metal methoxides, with high d counts preferred. Notably, early-to-middle metals tend toward oxidative hydrogen migration and late metals undergo a pathway that is more akin to σ-bond metathesis, suggesting that metal methoxide complexes that favor σ-bond metathesis pathways for methane activation will yield lower barriers for C–H activation.