Nucleophilic Reactivity of a Metal-Bound Superoxide Ligand
Nucleophilic Reactivity of a Metal-Bound Superoxide Ligand
复制标题
金属结合的超氧化物配体的亲核反应性
DOI：
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发表时间：
2015
期刊：
影响因子：
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通讯作者：
A. McDonald
中科院分区：
文献类型：
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作者：
Andrew D. Ure;A. McDonald
摘要金属-超氧化物物种经常被认为是双氧激活金属酶的瞬时中间体。金属结合的超氧化物部分已被提出既作为亲电试剂又作为亲核试剂反应。一般来说，模拟金属酶功能的模型复合物已被证明作为亲电试剂反应，并且没有显示出亲核反应性。在此，我们强调了我们小组最近的一项贡献，其中我们证明了金属超氧化物作为亲核试剂的第一个明确定义的例子。我们已经表明了铜超氧化物物种进行各种醛的亲核脱乙酰基的倾向。在这样做的过程中，我们已经为铁（III）-超氧化物在α-酮戊二酸依赖性双加氧酶等中作为亲核试剂反应的假定作用提供了实验支持。
Abstract Metal–superoxide species have frequently been implicated as transient intermediates in dioxygen activating metalloenzymes. The metal-bound superoxide moiety has been proposed to react both as an electrophile and a nucleophile. In general, model complexes that mimic metalloenzyme function have been shown to react as electrophiles, and none have displayed nucleophilic reactivity. Herein, we highlight a recent contribution from our group in which we demonstrated the first well-defined example of a metal–superoxide acting as a nucleophile. We have shown the propensity for a copper-superoxide species to perform nucleophilic deformylation of various aldehydes. In doing so, we have provided experimental support for the postulated role of an iron(III)–superoxide reacting as a nucleophile in the α-ketoglutarate-dependent dioxygenases amongst others.