非血红素铁(III)过氧化物配合物导致硫的氧化。
A Nonheme Iron(III) Superoxide Complex Leads to Sulfur Oxygenation.
机构信息
Department of Chemistry, The Johns Hopkins University, 3400 North Charles Street, Baltimore, Maryland 21218, United States.
Department of Chemical Physiology and Biochemistry, Oregon Health & Science University, Portland, Oregon 97239, United States.
出版信息
J Am Chem Soc. 2024 Mar 27;146(12):7915-7921. doi: 10.1021/jacs.3c12337. Epub 2024 Mar 15.
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.
摘要
报道了一种新型的含巯基配体的非血红素铁配合物 Fe(BNPAS)Br()。在-40°C 下，与 O 反应，或在-80°C 下，用 O 处理三价铁形式的，得到一个罕见的铁（III）-超氧自由基中间体Fe(O)(BNPAS)，其特征为 UV-vis、Fe Mössbauer、ATR-FTIR、EPR 和 CSIMS。然后，不稳定的通过涉及铁亚磺酸盐中间体的顺序 O 原子转移机制转化为 S-氧合铁（亚磺酸盐）产物。这些结果为硫醇双加氧酶中提出的中间体的可行性提供了证据。
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