A Nonheme Iron(III) Superoxide Complex Leads to Sulfur Oxygenation

Overview

Journal J Am Chem Soc

Publisher American Chemical Society

Specialty Chemistry

Date 2024 Mar 15

PMID 38488295

Authors

Sudha Yadav

Vishal Yadav

Maxime A Siegler

Pierre Moenne-Loccoz

Guy N L Jameson

David P Goldberg

Affiliations

Soon will be listed here.

Abstract

A new alkylthiolate-ligated nonheme iron complex, Fe(BNPAS)Br (), is reported. Reaction of with O at -40 °C, or reaction of the ferric form with O at -80 °C, gives a rare iron(III)-superoxide intermediate, [Fe(O)(BNPAS)] (), characterized by UV-vis, Fe Mössbauer, ATR-FTIR, EPR, and CSIMS. Metastable then converts to an S-oxygenated Fe(sulfinate) product via a sequential O atom transfer mechanism involving an iron-sulfenate intermediate. These results provide evidence for the feasibility of proposed intermediates in thiol dioxygenases.

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