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Speciation in iron epoxidation catalysis: A perspective on the discovery and role of non-heme iron(III)-hydroperoxo species in iron-catalyzed oxidation reactions
Coordination Chemistry Reviews ( IF 20.6 ) Pub Date : 2017-10-06 , DOI: 10.1016/j.ccr.2017.09.015
Sebastian M. Hölzl , Philipp J. Altmann , Jens W. Kück , Fritz E. Kühn

Oxidation reactions catalyzed by enzymes with central iron atoms are essential to life. The nature of these systems has evoked great interest to understand and model their reactivity. Considerable efforts have been made to elucidate the mechanisms that underlie the catalytic transformations. Many simplified, mononuclear model systems are known that allow for the spectroscopic and crystallographic characterization of intermediates relevant to this chemistry, such as iron(IV)-oxo, iron(V)-hydroxo oxo, iron(III)-peroxo, or iron(III)-superoxo complexes. One of the less researched, but still very decisive species is the iron(III)-hydroperoxo moiety that is assumed to be a crucial part of catalytic cycles during oxidation reactions with agents such as hydrogen peroxide, superoxides, or molecular oxygen. Although its molecular structure has not been resolved yet, a multitude of spectroscopic data unequivocally supports the existence of the hydroperoxo ligated iron center and its essential role in oxidation catalysis. The comprehension of the catalytic processes led to the development of powerful homogeneous catalysts for different oxidative conversions, such as dihydroxylation and epoxidation reactions.

中文翻译:

铁环氧化催化反应中的形态:非血红素铁(III)-氢过氧物质在铁催化的氧化反应中的发现及其作用的观点

具有中心铁原子的酶催化的氧化反应对生命至关重要。这些系统的性质引起了人们极大的兴趣来理解和建模其反应性。为了阐明催化转化基础的机理,已经做出了相当大的努力。已知有许多简化的单核模型系统,可对与该化学有关的中间体进行光谱和晶体学表征,例如铁(IV)-氧代,铁(V)-羟基氧代,铁(III)-过氧或铁( III)-超氧配合物。研究较少但仍具有决定性的物质之一是铁(III)-氢过氧部分,被认为是与试剂(例如过氧化氢,超氧化物或分子氧)发生氧化反应过程中催化循环的关键部分。尽管其分子结构尚未解析,但许多光谱数据明确支持氢过氧连接的铁中心的存在及其在氧化催化中的重要作用。对催化过程的理解导致了用于不同氧化转化,例如二羟基化和环氧化反应的功能强大的均相催化剂的发展。
更新日期:2017-10-06
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