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Direct Reduction of NO to N₂O by a Mononuclear Nonheme Thiolate Ligated Iron(II) Complex via Formation of a Metastable {FeNO}⁷ Complex.

ABSTRACT: Addition of NO to a nonheme dithiolate-ligated iron(II) complex, Fe^II(Me₃TACN)(S₂SiMe₂) (1), results in the generation of N₂O. Low-temperature spectroscopic studies reveal a metastable six-coordinate {FeNO}⁷ intermediate (S = 3/2) that was trapped at -135 °C and was characterized by low-temperature UV-vis, resonance Raman, EPR, Mössbauer, XAS, and DFT studies. Thermal decay of the {FeNO}⁷ species leads to the evolution of N₂O, providing a rare example of a mononuclear thiolate-ligated {FeNO}⁷ that mediates NO reduction to N₂O without the requirement of any exogenous electron or proton sources.

SUBMITTER: Dey A

PROVIDER: S-EPMC9555345 | biostudies-literature | 2022 Sep

REPOSITORIES: biostudies-literature

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Direct Reduction of NO to N2O by a Mononuclear Nonheme Thiolate Ligated Iron(II) Complex via Formation of a Metastable {FeNO}7 Complex.

Dey Aniruddha A Albert Therese T Kong Richard Y RY MacMillan Samantha N SN Moënne-Loccoz Pierre P Lancaster Kyle M KM Goldberg David P DP

Inorganic chemistry 20220915 38

Addition of NO to a nonheme dithiolate-ligated iron(II) complex, FeII(Me3TACN)(S2SiMe2) (1), results in the generation of N2O. Low-temperature spectroscopic studies reveal a metastable six-coordinate {FeNO}7 intermediate (S = 3/2) that was trapped at -135 °C and was characterized by low-temperature UV-vis, resonance Raman, EPR, Mössbauer, XAS, and DFT studies. Thermal decay of the {FeNO}7 species leads to ...[more]

PMID: 36107151

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