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首页> 外文期刊>Journal of biological inorganic chemistry: JBIC: a publication of the Society of Biological Inorganic Chemistry >Session lectures-High-valent metal-oxo and imido cores in chemistry and biology
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Session lectures-High-valent metal-oxo and imido cores in chemistry and biology

机译：会议讲座-化学和生物学中的高价金属-氧代和亚氨基核心

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Although terminal Co~(IV)–O, Ni_(III)–O and Cu_(III)–O intermediates have been implicated as active intermediates in a number of important chemical transformations, no spectroscopic evidences for the species are available, leaving the pathway uncertain [1,2]. Evidences of the presence of terminal M–O units [M = Cu(III), Ni(III) or Co(IV)] are to date limited to mass spectrometric studies in the gas phase [2]. Theory suggests that they should be powerful oxidants [2], perhaps even more reactive than the related [Fe_(IV)=O]~(2+) units that have been extensively studied [3]. In this presentation, we will summarize some of our recent efforts to stabilize the elusive metal-oxo and isoelectronic metal-imido units of Cu(III), Co(IV) [4] and Ni(III) [5]) in solution phase at low temperatures. The high-valent metal-oxo or metal-imido assignments are made on the basis of a variety of spectroscopic methods. The reactivity of the intermediates in hydrogen atom abstraction and oxo transfer reactions are also discussed.
机译：尽管末端Co〜（IV）–O，Ni_（III）–O和Cu_（III）–O中间体已被认为是许多重要化学转化中的活性中间体，但尚无该物种的光谱学证据，因此可以通过不确定[1,2]。迄今为止，存在末端M–O单元[M = Cu（III），Ni（III）或Co（IV）]的证据仅限于气相中的质谱研究[2]。理论表明，它们应该是强氧化剂[2]，甚至比已经被广泛研究的相关[Fe_（IV）= O]〜（2+）单元更具活性[3]。在此演示文稿中，我们将总结一些我们最近在溶液相中稳定Cu（III），Co（IV）[4]和Ni（III）[5]）的难溶金属-氧代和等电子金属-亚氨基单元的努力在低温下。高价金属-氧代或金属-亚氨基的分配是基于多种光谱方法进行的。还讨论了中间体在氢原子提取和氧代转移反应中的反应性。

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