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

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.

Graphical abstractA 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: [M]–OtBu + RNH2 → [M]–NHR + tBuOH (M = Co, Ni, Cu, Zn; R = H, Ph, Ad (Ad = 1-adamantyl), [M] = nacnac complex).Figure optionsDownload full-size imageDownload as PowerPoint slide