Rhodium(0) metalloradicals in binuclear C-H activation.

A reactive rhodium(0) metalloradical capable of binuclear activation of an aromatic C-H bond of PPh(3) 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 Rh(0) metalloradicals potentially produces kinetically labile Rh(I)-aryl and Rh(I)-H species, and thus, this could become a viable new approach to hydrocarbon functionalization.