High-valent iron and manganese complexes of corrole and porphyrin in atom transfer and dioxygen evolving catalysis
High-valent iron and manganese complexes of corrole and porphyrin in atom transfer and dioxygen evolving catalysis
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DOI：
10.1039/c0dt01341b
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发表时间：
2011-01-01
影响因子：
4
通讯作者：
Abu-Omar, Mahdi M.
中科院分区：
文献类型：
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作者：
Abu-Omar, Mahdi M.
通过Mn-Ⅲ（tpfc）与有机叠氮化合物光解或热活化生成的有机氮烯反应，合成了5，10，15-三（五氟苯基）咔咯（H（3）tpfc）的锰（V）亚胺配合物。锰（V）的末端亚氨基络合物是文献中Mn-V末端亚氨基络合物的第一个结构表征的实例。它们具有短的Mn-N三键和近线性的Mn-C角。（tpfc）Mn-V（NAr）的基态为单重态。与预期相反，锰（V）的芳基酰亚胺络合物对水分稳定，并且不经历[NR]基团向烯烃的转移。以碘代亚胺（ArINT）和锰（III）可咯为原料，合成了具有活化的对甲苯磺酰亚胺配体的锰（V）可咯。所得配合物（tpfc）Mn（NTs）具有顺磁性（S = 1），在水存在下水解为（tpfc）Mn（O），从苄基C-H键上夺取氢原子，并催化烯烃的氮丙啶化反应。综述了氮杂环丙烷化反应和氢原子转移反应的机理研究。这一观点还描述了血红素酶的反应化学，双氧形成在一个单一的金属网站的机制，以及这种酶的功能建模的最新进展。我们还比较了水溶性的铁与锰卟啉的反应性，对pH 4阴离子。
Manganese(V) imido complexes of 5,10,15-tris(pentafluorophenyl) corrole (H(3)tpfc) can be prepared by the reaction of Mn-III(tpfc) and organic nitrene generated from either photolytic or thermal activation of organic azides. The terminal imido complexes of manganese(V) were among the first structurally characterized examples of Mn-V terminal imido complexes in the literature. They feature a short Mn N triple bond and a nearly linear M N-C angle. The ground state of (tpfc) Mn-V(NAr) is singlet. Contrary to expectations, arylimido complexes of manganese(V) were stable to moisture and did not undergo [NR] group transfer to olefins. Manganese(V) imido corrole with an activated tosyl imido ligand was prepared from iodoimine (ArINTs) and manganese(III) corrole. The resulting complex (tpfc) Mn(NTs) is paramagnetic (S = 1), hydrolyzes to (tpfc)Mn(O) in the presence of water, abstracts hydrogen atoms from benzylic C-H bonds, and catalyzes aziridination of alkenes. Mechanistic studies on the aziridination and hydrogen atom transfer reactions are reviewed. This perspective also describes the reaction chemistry of the heme enzyme chlorite dismutase, the mechanism by which dioxygen is formed on a single-metal site, and recent advances in functional modelling of this enzyme. We also compare the reactivity of water-soluble iron versus manganese porphyrins towards the chlorite anion.