Unifying Evaluation of the Technical Performances of Iron-Tetra-amido Macrocyclic Ligand Oxidation Catalysts.

The main features of iron-tetra-amido macrocyclic ligand complex (a sub-branch of TAML) catalysis of peroxide oxidations are rationalized by a two-step mechanism: Fe(III) + H2O2 → Active catalyst (Ac) (kI), and Ac + Substrate (S) → Fe(III) + Product (kII). TAML activators also undergo inactivation under catalytic conditions: Ac → Inactive catalyst (ki). The recently developed relationship, ln(S0/S∞) = (kII/ki)[Fe(III)]tot, where S0 and S∞ are [S] at time t = 0 and ∞, respectively, gives access to ki under any conditions. Analysis of the rate constants kI, kII, and ki at the environmentally significant pH of 7 for a broad series of TAML activators has revealed a 6 orders of magnitude reactivity differential in both kII and ki and 3 orders differential in kI. Linear free energy relationships linking kII with ki and kI reveal that the reactivity toward substrates is related to the instability of the active TAML intermediates and suggest that the reactivity in all three processes derives from a common electronic origin. The reactivities of TAML activators and the horseradish peroxidase enzyme are critically compared.