Catalytic and Stoichiometric Baeyer-Villiger Oxidation Mediated by Nonheme Peroxo-Diiron(III), Acylperoxo, and Iodosylbenzene Iron(III) Intermediates.

In this paper we describe a detailed mechanistic studies on the [FeII(PBO)2(CF3SO3)2] (1), [FeII(PBT)2(CF3SO3)2] (2), and [FeII(PBI)3](CF3SO3)2 (3)-catalyzed (PBO = 2-(2'-pyridyl)benzoxazole, PBT = 2-(2'-pyridyl)benzthiazole, PBI = 2-(2'-pyridyl)benzimidazole) Baeyer-Villiger oxidation of cycloketones by dioxygen with cooxidation of aldehydes and peroxycarboxylic acids, including the kinetics on the reactivity of (µ-1,2-peroxo)diiron(III), acylperoxo- and iodosylbenzene-iron(III) species as key intermediates.

Functional models of nonheme diiron enzymes: kinetic and computational evidence for the formation of oxoiron(iv) species from peroxo-diiron(iii) complexes, and their reactivity towards phenols and H2O2.

The reactivity of the previously reported peroxo adducts [Fe2(µ-O2)(L(1))4(CH3CN)2](2+), and [Fe2(µ-O2)(L(2))4(CH3CN)2](2+), (L(1) = 2-(2'-pyridyl)benzimidazole and L(2) = 2-(2'-pyridyl)-N-methylbenzimidazole) towards H2O2 as catalase mimics, and towards various phenols as functional RNR-R2 mimics, is described. Kinetic, mechanistic and computational studies gave direct evidence for the involvement of the (µ-1,2-peroxo)diiron(iii) intermediate in the O-H activation process via formation of low-spin oxoiron(iv) species.