Rhodium(0) Metalloradicals in Binuclear C-H Activation

A reactive rhodium(0) metalloradical capable of binuclear activation of an aromatic C-H bond of PPh3 is disclosed. Kinetic measurements and density functional theory calculations reveal a binuclear mechanism: two metalloradicals add to a 'double bond' of the aromatic substrate while approaching the rate limiting C-H activation step (TS). Such aromatic C-H bond activation with Rho metalloradicals potentially produces kinetically labile Rh-1-aryl and Rh-1-H species, and thus, this could become a viable new approach to hydrocarbon functionalization.