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

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

doi:10.1021/acs.inorgchem.4c03802

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

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

^*Corresponding author for this work

Research School of Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

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.

Original language	English
Pages (from-to)	21313-21322
Number of pages	10
Journal	Inorganic Chemistry
Volume	63
Issue number	44
DOIs	https://doi.org/10.1021/acs.inorgchem.4c03802
Publication status	Published - 2024

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title = "Proton-Coupled Electron Transfer between a Pendant Thiol and a Ferrous Dioxygen Adduct",

abstract = "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.",

author = "Souvik Dinda and Triparna Roy and Soumya Samanta and Kumarjit Banerjee and Nicholas Cox and Abhishek Dey",

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doi = "10.1021/acs.inorgchem.4c03802",

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T1 - Proton-Coupled Electron Transfer between a Pendant Thiol and a Ferrous Dioxygen Adduct

AU - Dinda, Souvik

AU - Roy, Triparna

AU - Samanta, Soumya

AU - Banerjee, Kumarjit

AU - Cox, Nicholas

AU - Dey, Abhishek

PY - 2024

Y1 - 2024

N2 - 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.

AB - 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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DO - 10.1021/acs.inorgchem.4c03802

M3 - Article

C2 - 39432325

AN - SCOPUS:85207308772

SN - 0020-1669

VL - 63

SP - 21313

EP - 21322

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 44

ER -

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

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