Modeling of late 3d transition metal metathesis of tert-butoxide complexes with amines

Abstract

A DFT study of the alkoxide/amide metathesis reaction for late 3d transition metal β-diketiminate (nacnac) tert-butoxide and amide (N(H)R) complexes was performed. Bond dissociation free energies were used to understand trends in the reaction [M]–OtBu+RNH2→[M]–NHR+tBuOH (M=Co, Ni, Cu, Zn; R=H, Ph, Ad (Ad=1-adamantyl), [M]=nacnac complex). Steric effects were assessed via a multi-layer ONIOM approach for larger, more experimentally relevant substituents.