Generation and Reactivity of a Ni III 2 (μ-1,2-peroxo) Complex
Generation and Reactivity of a Ni III 2 (μ-1,2-peroxo) Complex
复制标题
Ni III 2 (μ-1,2-peroxo) 配合物的生成和反应性
DOI：
10.1021/jacs.0c10958
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发表时间：
2020
影响因子：
15
通讯作者：
Anderson, John S.
中科院分区：
文献类型：
--
作者：
Zhao, Norman;Filatov, Alexander S.;Xie, Jiaze;Hill, Ethan A.;Rogachev, Andrey Yu.;Anderson, John S.
高价过渡金属-氧代、-过氧和-超氧配合物是有机底物生物和合成氧化、水氧化和氧还原中的重要中间体。虽然Mn、Fe、Co和Cu的高价含氧络合物越来越为人们所熟知，但高价含氧Ni络合物相对较少。本文报道了在热不稳定的NiIII 2（μ-1，2-peroxo）配合物中分离出这样一种不寻常的高价物种，其特征在于使用单晶X-射线衍射和X-射线吸收，NMR和UV-vis光谱。反应性研究表明，这种复合物对氧的解离是稳定的，但与简单的亲核试剂和亲电试剂反应。
High-valent transition metal–oxo, −peroxo, and −superoxo complexes are crucial intermediates in both biological and synthetic oxidation of organic substrates, water oxidation, and oxygen reduction. While high-valent oxygenated complexes of Mn, Fe, Co, and Cu are increasingly well-known, high-valent oxygenated Ni complexes are comparatively rarer. Herein we report the isolation of such an unusual high-valent species in a thermally unstable NiIII2(μ-1,2-peroxo) complex, which has been characterized using single-crystal X-ray diffraction and X-ray absorption, NMR, and UV–vis spectroscopies. Reactivity studies show that this complex is stable toward dissociation of oxygen but reacts with simple nucleophiles and electrophiles.