Kinetico-Mechanistic Studies on a Reactive Organocopper(II) Complex: Cu-C Bond Homolysis versus Heterolysis

Organocopper(II) reagents are an unexplored frontier of copper catalysis. Despite being proposed as reactive intermediates, an understanding of the stability and reactivity of the Cu^II-C bond has remained elusive. Two main pathways can be considered for the cleavage mode of a Cu^II-C bond: homolysis and heterolysis. We recently showed how organocopper(II) reagents can react with alkenes via radical addition, a homolytic pathway. In this work, the decomposition of the complex [Cu^IILR]⁺ [L = tris(2- dimethylaminoethyl)amine, Me₆tren, R = NCCH₂^-] in the absence and presence of an initiator (RX, X = Cl, Br) was evaluated. When no initiator was present, first-order Cu^II-C bond homolysis occurred producing [Cu^IL]⁺ and succinonitrile, via radical termination. When an excess of the initiator was present, a subsequent formation of [Cu^IILX]⁺ via a second-order reaction was found, which results from the reaction of [Cu^IL]⁺ with RX following homolysis. However, when Brønsted acids (R'-OH: R' = H, Me, Ph, PhCO) were present, heterolytic cleavage of the Cu^II-C bond produced [Cu^IIL(OR')]⁺ and MeCN. Kinetic studies were undertaken to obtain the thermal (ΔH^⧧, ΔS^⧧) and pressure (ΔV^⧧) activation parameters and deuterium kinetic isotopic effects, which provided an understanding of the strength of the Cu^II-C bond and the nature of the transition state for the reactions involved. These results reveal possible reaction pathways for organocopper(II) complexes relevant to their applications as catalysts in C-C bond forming reactions.