Who wins: Pesci, peters, or deacon? Intrinsic reactivity orders for organocuprate formation via ligand decomposition

Abstract

There are three metal-mediated ligand decomposition reactions that give rise to organometallics: (i) decarboxylation of a metal carboxylate, "the Pesci reaction"; (ii) desulfination of a metal sulfinate, "the Peters reaction"; (iii) desulfonation of a metal sulfonate, "the Deacon reaction". Despite growing interest in their use in applications in organic synthesis, little is known about the relative ease of thermal extrusion of CO 2 versus SO 2 versus SO 3 in metal complexes. Here the intrinsic reactivity orders for organocuprate formation via ligand decomposition have been studied in the gas phase for the first time. A combination of low-energy collision-induced dissociation experiments in ..