Transition metal complexes and the activation of dioxygen.
Transition metal complexes and the activation of dioxygen.
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DOI：
10.1007/978-3-319-12415-5_5
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发表时间：
2015
期刊：
影响因子：
--
通讯作者：
Gereon M Yee;W. Tolman
中科院分区：
文献类型：
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作者：
Gereon M Yee;W. Tolman
为了解决如何不同的金属蛋白活性位点，特别是那些含有铁和铜，指导O2结合和激活过程，以执行不同的功能，活性位点的合成模型的研究已经进行。这些研究导致了深刻的，基本的化学见解O2如何协调单核和多核Fe和Cu中心，并减少到superoxo，过氧，氢过氧，并在O-O键断裂后，氧物种相关的催化中间体。最近的进展，了解各种因素的影响过程中的O2活化的Fe和Cu配合物的调查，重点评估的结构，键合，和反应性的中间体。讨论是由一个总体的机制范式，由于不同的金属离子，核，几何形状和支持配体的参与提供了丰富的挂毯的反应途径，O2被激活在Fe和Cu网站的详细差异。
In order to address how diverse metalloprotein active sites, in particular those containing iron and copper, guide O2binding and activation processes to perform diverse functions, studies of synthetic models of the active sites have been performed. These studies have led to deep, fundamental chemical insights into how O2coordinates to mono- and multinuclear Fe and Cu centers and is reduced to superoxo, peroxo, hydroperoxo, and, after O-O bond scission, oxo species relevant to proposed intermediates in catalysis. Recent advances in understanding the various factors that influence the course of O2activation by Fe and Cu complexes are surveyed, with an emphasis on evaluating the structure, bonding, and reactivity of intermediates involved. The discussion is guided by an overarching mechanistic paradigm, with differences in detail due to the involvement of disparate metal ions, nuclearities, geometries, and supporting ligands providing a rich tapestry of reaction pathways by which O2is activated at Fe and Cu sites.