Carbon-hydrogen versus carbon-heteroatom activation by a high-valent zirconium-imido complex

摘要

A density functional theory (DFT) study of carbon-hydrogen versus carbon-heteroatom bond activation is presented. Heteroatom groups (X) investigated include X = F, Cl, OH, SH, NH2, PH2. The activating model complex is a prototypical d(0) zirconium-imide. While C-X activation has a thermodynamic advantage over C-H activation, the former has been found to have a kinetic advantage. Implications for catalytic hydrocarbon functionalization and phosphine-ligand degradation are discussed. The present results for a high-valent metal complex are compared/contrasted with low-valent bond activating complexes.