Abstract
The reductive activation of molecular oxygen catalyzed by iron-based enzymes toward its use as an oxygen donor is paradigmatic for oxygen transfer reactions in nature. Mechanistic studies on these ...
Highlights
Iron-based monooxygenase enzymes have diverse structures and active site configurations, and different biological roles and different target substrates.[1]Despite this diversity in structure and biological function, they have many common mechanistic similarities
We had already previously observed that an iron−tungsten capsule, {FeIII30WVI72}, was able to cathodically activate O2 leading to interesting transformations such as the oxidation of ethane to acetic acid at ambient conditions, low potentials, and in water.[13]
This Article reports on some mechanistic details concerning the catalytic cycle of this reaction
Summary
Iron-based monooxygenase enzymes have diverse structures and active site configurations, and different biological roles and different target substrates.[1]. Ascorbate was used as reductant to activate O2 over a diiron complex, but the reaction was substoichiometric.[8] Cathodic electrocatalytic reactions present intriguing possibilities for the activation of O2 In this context, early use of manganese(III) porphyrins showed low activity,[9] and an electrocatalytic alkane oxidation with cytochrome P-450 failed allowing only the more facile sulfide oxidation.[10] In the past few years there have been 3 reports of cathodic activation of O2 toward C H bond hydroxylation and alkene epoxidation based on iron catalysts. Beyond the alkane and alkene oxidations noted above, the previous research on electrocatalytic oxidation with {FeIII30WVI72} revealed by cyclic voltammetry that (a) the yellow {FeIII30WVI72} compound shows a fast, reversible, diffusion limited reduction of Fe(III) to Fe(II) at 0.47 V vs. Ag/AgCl; (b) at 0 V vs Ag/AgCl the capsule is reduced by 10 electrons, yielding a brown {FeII10FeIII30WVI72} species, commensurate with one reduced iron atom, Fe(II), per pore. I type active intermediate species is formed in the catalytic cycle that explains the activity of {Fe30W72} in cathodic aerobic oxidation reactions
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