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

Sudha Yadav; Vishal Yadav; Maxime A. Siegler; Pierre Moënne-Loccoz; Guy N.L. Jameson; David P. Goldberg

doi:10.1021/jacs.3c12337

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

Sudha Yadav, Vishal Yadav, Maxime A. Siegler, Pierre Moënne-Loccoz, Guy N.L. Jameson, David P. Goldberg

Chemical Physiology and Biochemistry

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

Abstract

A new alkylthiolate-ligated nonheme iron complex, Fe^II(BNPA^Me2S)Br (1), is reported. Reaction of 1 with O₂ at −40 °C, or reaction of the ferric form with O₂^•- at −80 °C, gives a rare iron(III)-superoxide intermediate, [Fe^III(O₂)(BNPA^Me2S)]⁺ (2), characterized by UV-vis, ⁵⁷Fe Mössbauer, ATR-FTIR, EPR, and CSIMS. Metastable 2 then converts to an S-oxygenated Fe^II(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.

Original language	English (US)
Pages (from-to)	7915-7921
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	146
Issue number	12
DOIs	https://doi.org/10.1021/jacs.3c12337
State	Published - Mar 27 2024

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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abstract = "A new alkylthiolate-ligated nonheme iron complex, FeII(BNPAMe2S)Br (1), is reported. Reaction of 1 with O2 at −40 °C, or reaction of the ferric form with O2•- at −80 °C, gives a rare iron(III)-superoxide intermediate, [FeIII(O2)(BNPAMe2S)]+ (2), characterized by UV-vis, 57Fe M{\"o}ssbauer, ATR-FTIR, EPR, and CSIMS. Metastable 2 then converts to an S-oxygenated FeII(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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AU - Yadav, Sudha

AU - Yadav, Vishal

AU - Siegler, Maxime A.

AU - Moënne-Loccoz, Pierre

AU - Jameson, Guy N.L.

AU - Goldberg, David P.

PY - 2024/3/27

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N2 - A new alkylthiolate-ligated nonheme iron complex, FeII(BNPAMe2S)Br (1), is reported. Reaction of 1 with O2 at −40 °C, or reaction of the ferric form with O2•- at −80 °C, gives a rare iron(III)-superoxide intermediate, [FeIII(O2)(BNPAMe2S)]+ (2), characterized by UV-vis, 57Fe Mössbauer, ATR-FTIR, EPR, and CSIMS. Metastable 2 then converts to an S-oxygenated FeII(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.

AB - A new alkylthiolate-ligated nonheme iron complex, FeII(BNPAMe2S)Br (1), is reported. Reaction of 1 with O2 at −40 °C, or reaction of the ferric form with O2•- at −80 °C, gives a rare iron(III)-superoxide intermediate, [FeIII(O2)(BNPAMe2S)]+ (2), characterized by UV-vis, 57Fe Mössbauer, ATR-FTIR, EPR, and CSIMS. Metastable 2 then converts to an S-oxygenated FeII(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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A Nonheme Iron(III) Superoxide Complex Leads to Sulfur Oxygenation

Abstract

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