title: Methane C-H bond activation by "naked" alkali metal imidyl and alkaline earth metal imide complexes. The role of ligand spin and nucleophilicity.
abstract: High accuracy correlation consistent Composite Approach (ccCA) calculations have been used to investigate methane C-H bond activation with alkali metal imidyl and alkaline earth metal imide complexes. Alkali metals (Li, Na) and alkaline earth metals (Be, Mg) are used in this research given their redox innocence, namely, M(+) and M(2+), respectively. The ccCA calculations for methane activation by imidyl radical NH(•-) and triplet nitrene NH(••) show a thermodynamic (ΔΔH = 13.2 kcal/mol) and kinetic (ΔΔH(‡) = 15.9 kcal/mol) preference for the former. Methane activation by LiNH(•) and MgNH proceeds via hydrogen atom abstraction (HAA) and [2 + 2] transition states; only HAA pathways are isolated for NaNH and BeNH. The ccCA computed enthalpies lead to the hypothesis that the nucleophilicity of the nitrogen of the activating ligand (NR) is the key ingredient in activating the strongest sp(3) C-H bonds like that of methane.
authors: Center for Catalytic Hydrocarbon Functionalization (CCHF), Department of Chemistry, Center for Advanced Scientific Computing and Modeling (CASCaM), University of North Texas , 1155 Union Circle, #305070, Denton, Texas 76203-5017, United States.
authors: Bruce M
authors: BM
authors: Prince
authors: Thomas R
authors: TR
authors: Cundari