Transition state energy decomposition study of Acetate-Assisted and internal electrophilic substitution C-H Bond activation by (acac-O,O) ₂Ir(X) complexes (X = CH ₃COO, OH)

Chelate-assisted and internal electrophilic substitution type transition states were studied using a DFT-based energy decomposition method. Interaction energies for benzene and methane C-H bond activation by (acac-O,O) ₂Ir(X) complexes (X = CH ₃COO and OH) were evaluated using the absolutely localized molecular orbital energy decomposition analysis (ALMO-EDA). A ratio of ∼1.5:1 for forward to reverse charge-transfer between (acac-O,O) ₂Ir(X) and benzene or methane transition state fragments confirms "ambiphilic" bonding, the result of an interplay between the electrophilic iridium center and the internal base component. This analysis also revealed that polarization effects account for a significant amount of transition state stabilization. The energy penalty to deform reactants into their transition state geometry, distortion energy, was also used to understand the large activation energy difference between six-membered and four-membered acetate-assisted transition states and help explain why these complexes do not activate the methane C-H bond.