Experimental and theoretical evidence for multiple FeIV reactive intermediates in TAML-activator catalysis: Rationalizing a counterintuitive reactivity order

Abstract

Reacting rationally
During the 1e oxidation of ferrocyanide by the catalytic TAML activator and H₂O₂, four Fe^IV tetra-amido macrocyclic ligand (TAML) intermediates were detected that are involved in a fast acid–base equilibrium. The counterintuitive reactivity pattern is explained by the overall free-energy change during the reduction of Fe^IV to Fe^III TAML complexes, with competing contributions from electronic and solvation energy changes.