Biological systems capitalize on the redox versatility of manganese to perform reactions involving dioxygen and its derivatives superoxide, hydrogen peroxide, and water. The reactions of manganese enzymes influence both human health and the global energy cycle. Important examples include the detoxification of reactive oxygen species by manganese superoxide dismutase, biosynthesis by manganese ribonucleotide reductase and manganese lipoxygenase, and water splitting by the oxygen-evolving complex of photosystem II. Although these enzymes perform very different reactions and employ structurally distinct active sites, manganese intermediates with peroxo, hydroxo, and oxo ligation are commonly proposed in catalytic mechanisms. These intermediates are also postulated in mechanisms of synthetic manganese oxidation catalysts, which are of interest due to the earth abundance of manganese. In this Account, we describe our recent efforts toward understanding O–O bond activation pathways of Mn^III-peroxo adducts and hydrogen-atom transfer reactivity of Mn^IV-oxo and Mn^III-hydroxo complexes.

中文翻译：

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锰-氧中间体在O-O键活化和氢原子转移反应中

生物系统利用锰的氧化还原多功能性来进行涉及双氧及其衍生物超氧化物，过氧化氢和水的反应。锰酶的反应会影响人类健康和全球能源循环。重要的例子包括锰超氧化物歧化酶对活性氧的解毒，锰核糖核苷酸还原酶和锰脂氧合酶的生物合成以及光系统II的放氧复合物分解水。尽管这些酶进行的反应非常不同，并且在结构上具有不同的活性位点，但在催化机理中通常提出了具有过氧，羟基和氧代连接的锰中间体。这些中间体也被认为是合成锰氧化催化剂的机理，由于锰在地球上的丰富性而受到关注。在本报告中，我们描述了我们最近为理解锰的O–O键激活途径所做的努力Mn ^IV-氧代和Mn ^III-羟基配合物的^III-过氧加合物和氢原子转移反应性。