Bonding and the role of electrostatics in driving C–C bond formation in high valent organocopper compounds

Abstract

The electronic structures and contrasting reactivity of [Cu(CF₃)₄]⁻ and [Cu(CF₃)₃(CH₃)]⁻ were probed using coupled cluster and ab initio valence bond calculations. The Cu–C bonds in these complexes were found to be charge shift bonds. A key finding is that electrostatics likely prevent [Cu(CF₃)₄]⁻ from accessing a productive transition state for C–C bond formation while promote one for [Cu(CF₃)₃(CH₃)]⁻. These results therefore highlight essential design criteria for Cu-mediated C–C/C–heteroatom bond formation.