垂体硫醇与亚铁二氧加合物之间的质子耦合电子转移

IF 4.3 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Pub Date : 2024-10-21 DOI:10.1021/acs.inorgchem.4c03802

Souvik Dinda, Triparna Roy, Soumya Samanta, Kumarjit Banerjee, Nicholas Cox, Abhishek Dey

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引用次数: 0

摘要

通过在低温下捕获转化的中间产物，并随后使用连续波和脉冲电子顺磁共振以及共振拉曼光谱对其进行表征，研究了亚铁卟啉催化的硫醇被 O2 氧化的机理。在带有悬挂硫醇官能团的铁卟啉中，最初会形成一个 Fe(III)-O2 -- 物种，该物种经过质子耦合电子转移（PCET）（非 HAT）形成一个 Fe(III)-OOH 物种。在 O-O 键均解之后，形成 Fe(IV)═O 物种，同时硫醇氧化成 RSO3H 基团。

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Proton-Coupled Electron Transfer between a Pendant Thiol and a Ferrous Dioxygen Adduct

The mechanism of thiol oxidation by O₂, as catalyzed by ferrous porphyrins, is investigated by trapping intermediates of the transformation at low temperatures and subsequently characterizing them using continuous wave and pulsed electron paramagnetic resonance and resonance Raman spectroscopy. A Fe(III)-O₂^•– species is initially formed in an iron porphyrin with a pendant thiol functional group, which undergoes proton-coupled electron transfer (PCET) (not HAT) to form an Fe(III)-OOH species. Following O–O bond homolysis, this forms a Fe(IV)═O species with concomitant oxidation of the thiol to an RSO₃H group.

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来源期刊

Inorganic Chemistry 化学-无机化学与核化学

CiteScore

7.60

自引率

13.00%

发文量

1960

审稿时长

1.9 months

期刊介绍： Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.