The Catalytic Role of Extra Molecules in the Aminolysis or Heterolytic Cleavage of an Iridium Alkoxycarbene Complex: Reactions of an Iridium Alkoxycarbene Complex

A theoretical analysis was performed on reactions involving iridium alkoxycarbene complex [IrCp*Cl{=C(OCH3)CHCPh2}(PPh2Me)]PF6 (Cp* = pentamethylcyclopentadienyl), which can undergo aminolysis or heterolytic cleavage of the carbon(sp3)–oxygen bond. The energy barriers of these pathways were estimated and the reasons for the reactivity of the system evaluated. Aminolysis or heterolytic cleavage of the carbon(sp3)–oxygen bond is the result of a subtle equilibrium between electronic, steric, and cooperative effects. Cooperative effects facilitate the proton transfer that occurs in aminolysis through formation of a bridge by one or several molecules. These molecules act as catalysts that decrease the energy barrier and change the favored pathway, so that the environment is a key factor in the reactivity of this complex.