AI Article Synopsis
- The novel Raman spectroscopic model focuses on a dinuclear iron site in ribonucleotide reductase and met-hemerythrin that effectively oxidizes hydrogen peroxide to dioxygen through an inner-sphere electron transfer process.
- The oxidation reaction leads to the formation of two deprotonated species in aqueous media, but these species do not participate in further oxidizing hydrogen peroxide.
- Kinetic analysis indicates the formation of a peroxo intermediate and suggests that proton-coupled electron transfer plays a key role in the rate-determining step of the redox reaction.
Article Abstract
A novel Raman spectroscopic model for the dinuclear iron site in ribonucleotide reductase and met-hemerythrin, [Fe2(micro-O)(phen)4(H2O)2]4+, 1, (phen = 1,10-phenanthroline) quantitatively oxidizes hydrogen peroxide to dioxygen via an inner-sphere electron transfer pathway. Although 1 deprotonates to form [Fe2(micro-O)(phen)4(H2O)(OH)]3+ (2) and [Fe2(micro-O)(phen)4(OH)2]2+ (3) in aqueous media, neither 2 nor 3 is reactive in oxidising H2O2. In the presence of excess phen, no phen-releasing equilibria from , and exist. Kinetic evidence of the generation of a (micro-1,2 peroxo)diiron(III,III) intermediate, prior to electron transfer, were obtained. Significant rate retardation in D2O media suggests proton coupled electron transfer (PCET) in the rate determining step of the title redox reaction.
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