Dioxygenation Reaction of a Cobalt-Nitrosyl: Putative Formation of a Cobalt–Peroxynitrite via a {CoIII(NO)(O2–)} Intermediate,Inorganic Chemistry

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Dioxygenation Reaction of a Cobalt-Nitrosyl: Putative Formation of a Cobalt–Peroxynitrite via a {CoIII(NO)(O2–)} Intermediate
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2017-11-13 00:00:00 , DOI: 10.1021/acs.inorgchem.7b01673
Kuldeep Gogoi ₁ , Soumen Saha ₁ , Baishakhi Mondal ₁ , Hemanta Deka ₁ , Somnath Ghosh ₁ , Biplab Mondal ₁

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A cobalt-nitrosyl complex, [(BPI)Co(NO)(OAc)], 1 {BPI = 1,3-bis(2′-pyridylimino)isoindol} was prepared and characterized. Structural characterization revealed that the cobalt center has a distorted square pyramidal geometry with the NO group coordinated from the apical position in a bent fashion. The addition of dioxygen (O₂) to the dichloromethane solution of complex 1 resulted in the formation of nitro complex, [(BPI)Co(NO₂)(OAc)], 2. It was characterized structurally. Kinetic studies suggested the involvement of an associative mechanism. FT-IR spectroscopic studies suggested the formation of the intermediate 1a [(BPI)Co^III(NO)(O₂^–)(OAc)] in the reaction. The intermediate 1a decomposed to complex 2 via a presumed peroxynitrite intermediate which was implicated by its characteristic phenol ring nitration reaction.

中文翻译：

钴-亚硝双氧化反应：通过钴-过氧亚硝酸盐的形成推定{钴^III（NO）（O ₂^-）}中间体

制备并表征了钴-亚硝酰基复合物[（BPI）Co（NO）（OAc）] 1 {BPI = 1,3-双（2'-吡啶基氨基）异吲哚}。结构表征表明，钴中心具有扭曲的方形棱锥几何形状，其中NO基团从顶端位置以弯曲的方式进行配位。向配合物1的二氯甲烷溶液中添加双氧（O ₂）导致形成硝基配合物[（BPI）Co（NO ₂）（OAc）] 2。它的结构特点。动力学研究表明涉及一种关联机制。FT-IR光谱研究表明中间体1a [（BPI）Co ^III（NO）（O ₂^–）（OAc）]。中间体1a通过假定的过氧亚硝酸盐中间体分解成配合物2，其特征在于其酚环硝化反应。

更新日期：2017-11-13

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