Effect of Ligand Connectivity and Charge State on the Amination of C–H Bonds by Copper Amide Complexes

Abstract

Activation of a benzylic C–H bond of indane by a copper(II) amide with various supporting ligands has been studied using density functional theory. Complexes with an overall charge of +1 are calculated to have lower activation barriers than neutral complexes. The effect on the activation barrier of the connectivity of the amide nitrogen—secondary (2-adamantyl) versus tertiary (1-adamantyl)—was also modeled. The calculations suggest that a combination of charge and steric factors at both the metal and nitrogen of the Cu–N active site have a considerable impact on the activation energy for copper(II) amide complexes but much less impact upon the thermodynamics. Correlations with other properties such as spin density and atomic charges are also reported.