Activation of Dioxygen by Iron and Manganese Complexes: A Heme and Nonheme Perspective.
Activation of Dioxygen by Iron and Manganese Complexes: A Heme and Nonheme Perspective.
复制标题
DOI：
10.1021/jacs.6b05251
复制
发表时间：
2016-09-14
影响因子：
15
通讯作者：
Goldberg DP
中科院分区：
文献类型：
--
作者：
Sahu S;Goldberg DP
对于合成无机化学家来说，合理设计定义良好的第一排过渡金属络合物以活化氧气一直是一个具有挑战性的目标。O2的激活很重要，部分原因是它在金属酶的功能中起着核心作用，金属酶利用O2执行一些具有挑战性的反应，包括各种底物的高度选择性氧化。在合成催化氧化系统中，利用O2这一丰富的、对环境友好的氧化剂也引起了极大的兴趣。这一视角汇集了最近的仿生铁和锰络合物的例子，这些络合物可以在血红素或非血红素类型的配体环境中激活O2。使用诸如高价碘(例如，Ario)、过氧酸(例如，m-CPBA)、过氧物(例如，H_2O_2)或甚至是超氧化物的氧化剂是访问特征良好的金属-超氧基、金属-过氧基或金属-氧基物种的流行选择，但与氧气反应以产生这种可观察到的金属-氧物种的仿生铁/锰络合物的实例令人惊讶地少。这一视角聚焦于表现出与O2反应并导致光谱可观察到的金属-氧物种和/或氧化生物相关底物的单核Fe和Mn络合物。对这些例子的分析表明，溶剂、自旋态、氧化还原电势、外部共还原剂和配体结构都可以在O2活化过程中发挥重要作用。
The rational design of well-defined, first-row transition metal complexes that can activate dioxygen has been a challenging goal for the synthetic inorganic chemist. The activation of O2 is important in part because of its central role in the functioning of metalloenzymes, which utilize O2 to perform a number of challenging reactions including the highly selective oxidation of various substrates. There is also great interest in utilizing O2, an abundant and environmentally benign oxidant, in synthetic catalytic oxidation systems. This Perspective brings together recent examples of biomimetic Fe and Mn complexes that can activate O2 in heme or nonheme-type ligand environments. The use of oxidants such as hypervalent iodine (e.g., ArIO), peracids (e.g., m-CPBA), peroxides (e.g., H2O2) or even superoxide is a popular choice for accessing well-characterized metal–superoxo, metal–peroxo, or metal–oxo species, but the instances of biomimetic Fe/Mn complexes that react with dioxygen to yield such observable metal–oxygen species are surprisingly few. This Perspective focuses on mononuclear Fe and Mn complexes that exhibit reactivity with O2 and lead to spectroscopically observable metal–oxygen species, and/or oxidize biologically relevant substrates. Analysis of these examples reveals that solvent, spin state, redox potential, external co-reductants, and ligand architecture can all play important roles in the O2 activation process.