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Biomimetic Reactivity of Oxygen-Derived Manganese and Iron Porphyrinoid Complexes
Chemical Reviews ( IF 51.4 ) Pub Date : 2017-10-09 00:00:00 , DOI: 10.1021/acs.chemrev.7b00180 Regina A. Baglia 1 , Jan Paulo T. Zaragoza 1 , David P. Goldberg 1
Chemical Reviews ( IF 51.4 ) Pub Date : 2017-10-09 00:00:00 , DOI: 10.1021/acs.chemrev.7b00180 Regina A. Baglia 1 , Jan Paulo T. Zaragoza 1 , David P. Goldberg 1
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Heme proteins utilize the heme cofactor, an iron porphyrin, to perform a diverse range of reactions including dioxygen binding and transport, electron transfer, and oxidation/oxygenations. These reactions share several key metalloporphyrin intermediates, typically derived from dioxygen and its congeners such as hydrogen peroxide. These species are composed of metal–dioxygen, metal–superoxo, metal–peroxo, and metal–oxo adducts. A wide variety of synthetic metalloporphyrinoid complexes have been synthesized to generate and stabilize these intermediates. These complexes have been studied to determine the spectroscopic features, structures, and reactivities of such species in controlled and well-defined environments. In this Review, we summarize recent findings on the reactivity of these species with common porphyrinoid scaffolds employed for biomimetic studies. The proposed mechanisms of action are emphasized. This Review is organized by structural type of metal–oxygen intermediate and broken into subsections based on the metal (manganese and iron) and porphyrinoid ligand (porphyrin, corrole, and corrolazine).
中文翻译：
氧衍生的锰铁卟啉配合物的仿生反应性
血红素蛋白利用血红素辅因子铁卟啉进行多种反应，包括双氧结合和转运，电子转移以及氧化/加氧。这些反应共有几种关键的金属卟啉中间体，这些中间体通常衍生自双氧及其同类物，例如过氧化氢。这些物质由金属-双氧，金属-超氧，金属-过氧和金属-氧加合物组成。已经合成了各种各样的合成金属类卟啉络合物以产生和稳定这些中间体。已经研究了这些配合物，以确定在受控和明确定义的环境中此类物质的光谱特征，结构和反应性。在这篇评论中，我们总结了这些物种与用于仿生研究的普通卟啉类支架的反应性的最新发现。强调了拟议的行动机制。本综述按金属-氧中间体的结构类型组织，并根据金属（锰和铁）和卟啉类配体（卟啉，corrole和corrolazine）分为小节。
更新日期：2017-10-09
中文翻译：
氧衍生的锰铁卟啉配合物的仿生反应性
血红素蛋白利用血红素辅因子铁卟啉进行多种反应，包括双氧结合和转运，电子转移以及氧化/加氧。这些反应共有几种关键的金属卟啉中间体，这些中间体通常衍生自双氧及其同类物，例如过氧化氢。这些物质由金属-双氧，金属-超氧，金属-过氧和金属-氧加合物组成。已经合成了各种各样的合成金属类卟啉络合物以产生和稳定这些中间体。已经研究了这些配合物，以确定在受控和明确定义的环境中此类物质的光谱特征，结构和反应性。在这篇评论中，我们总结了这些物种与用于仿生研究的普通卟啉类支架的反应性的最新发现。强调了拟议的行动机制。本综述按金属-氧中间体的结构类型组织，并根据金属（锰和铁）和卟啉类配体（卟啉，corrole和corrolazine）分为小节。
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