通过氢原子攫取，从其过氧自由基中间产物得到结构确证的非血红素钴-过氧配合物。
A Structurally Characterized Nonheme Cobalt-Hydroperoxo Complex Derived from Its Superoxo Intermediate via Hydrogen Atom Abstraction.
机构信息
Department of Chemistry and Instrumentation Center, National Taiwan Normal University , Taipei 11677, Taiwan.
Department of Chemistry, National Tsing Hua University , Hsinchu 30013, Taiwan.
出版信息
J Am Chem Soc. 2016 Nov 2;138(43):14186-14189. doi: 10.1021/jacs.6b08642. Epub 2016 Oct 20.
Bubbling O into a THF solution of Co(BDPP) (1) at -90 °C generates an O adduct, Co(BDPP)(O) (3). The resonance Raman and EPR investigations reveal that 3 contains a low spin cobalt(III) ion bound to a superoxo ligand. Significantly, at -90 °C, 3 can react with 2,2,6,6-tetramethyl-1-hydroxypiperidine (TEMPOH) to form a structurally characterized cobalt(III)-hydroperoxo complex, Co(BDPP)(OOH) (4) and TEMPO. Our findings show that cobalt(III)-superoxo species are capable of performing hydrogen atom abstraction processes. Such a stepwise O-activating process helps to rationalize cobalt-catalyzed aerobic oxidations and sheds light on the possible mechanism of action for Co-bleomycin.
将氧气鼓泡到 -90°C 的 Co(BDPP)(1)的四氢呋喃溶液中会生成一个 O 加合物，Co(BDPP)(O)(3)。共振拉曼和 EPR 研究表明，3 中含有一个低自旋的钴(III)离子与超氧配体结合。重要的是，在 -90°C 时，3 可以与 2,2,6,6-四甲基-1-羟基哌啶 (TEMPOH)反应，形成一个结构表征的钴(III)-过氧氢配合物 Co(BDPP)(OOH)(4)和 TEMPO。我们的发现表明，钴(III)-超氧物种能够进行氢原子提取过程。这种逐步的 O 激活过程有助于合理化钴催化的有氧氧化，并为 Co-bleomycin 的可能作用机制提供了线索。
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