Theoretical Estimation of Catalytic Reactivity as Iron-Oxygen Nano-Materials
With a view to understanding the reactivity of the μ-peroxo diiron(III) complexes in biological oxidation enzymes, such as soluble methane monooxygenase (sMMO) and ribonucleotide reductase (RNR), cis-μ-1,2- and trans-μ-1,2-peroxo diiron complexes were theroretically treated by the use of DFT calculation. Full-optimizations of the structures were carried out using the initial structures of (μ-O2-)(μ-CH3COO-)(μ-O2 2-)[FeIII(A3CY)]2 + and (μ-O2 2- )[FeIII(A3CY)Cl2]2 (A3CY = cis,cis-1,3,5-tris-amino-cyclohexane) for cis- and trans-forms, respectively, by minimizing their total energies. The O-O stretching vibrations were estimated for both isomers; the 16O-16O stretching frequencies for peroxo diiron complexes with cis- and transforms were 840 and 769 cm-1, respectively, which showed an isotope shift to 791 and 724 cm-1, respectively, by the use of 18O2 2- in the place of 16O2 2-. The structure/function relationship for them was discussed.
Masayuki Nogami, Riguang Jin, Toshihiro Kasuga and Wantai Yang
Y. Honda, H. Arii, T. Ozawa, Y. Funahashi, H. Masuda, "Theoretical Estimation of Catalytic Reactivity as Iron-Oxygen Nano-Materials", Advanced Materials Research, Vols. 11-12, pp. 339-342, 2006