Peroxomanganese complexes as an aid to understanding redox-active manganese enzymes
Peroxomanganese complexes as an aid to understanding redox-active manganese enzymes
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DOI：
10.1007/s00775-013-1067-4
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发表时间：
2013
期刊：
影响因子：
--
通讯作者：
Domenick F. Leto;Timothy A. Jackson
中科院分区：
文献类型：
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作者：
Domenick F. Leto;Timothy A. Jackson
在过去的 7 年里，有大量研究描述了合成过氧化锰加合物的结构和电子特性以及化学反应性。许多氧化还原活性锰酶，包括含锰超氧化物歧化酶、额外二醇儿茶酚双加氧酶和核糖核苷酸还原酶，被认为在其催化循环中具有过氧锰中间体的特征。因此，最近使用合成复合物模拟这些中间体的努力为酶的机理研究提供了强有力的补充。本综述提供了该领域工作的总结和展望，重点是 η2-过氧锰（III）和 η1-烷基过氧锰（III）加合物的几何和电子结构与化学反应性之间的关系。
Over the past 7 years, there have been a significant number of studies describing the structural and electronic properties, as well as the chemical reactivity, of synthetic peroxomanganese adducts. Many redox-active manganese enzymes, including manganese-containing superoxide dismutases, extradiol catechol dioxygenases, and ribonucleotide reductases, are proposed to feature peroxomanganese intermediates in their catalytic cycles. The recent efforts to model these intermediates using synthetic complexes have thus provided a strong complement to mechanistic studies of the enzymes. This review provides both a summary and a perspective of work in this area, with an emphasis on the relationship between geometric and electronic structure and chemical reactivity for η2-peroxomanganese(III) and η1-alkylperoxomanganese(III) adducts.