Ligand Field Effects and the High Spin-High Reactivity Correlation in the H Abstraction by Non-Heme Iron(IV)-Oxo Complexes: A DFT Frontier Orbital Perspective

Kazaryan Andranik; Baerends Evert Jan

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Ligand Field Effects and the High Spin-High Reactivity Correlation in the H Abstraction by Non-Heme Iron(IV)-Oxo Complexes: A DFT Frontier Orbital Perspective

机译：非血红素铁（IV）-氧配合物在H原子提取中的配体场效应和高自旋-高反应性相关：DFT前沿轨道视角

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The electronic structure explanation of H abstraction from aliphatic CH bonds by the ferryl ion, (FeO2+)-O-IV, has received a great deal of attention. We review the insights that have been gained, in particular into the effect of the spin state. However, we emphasize that the spin state is dictated by the field of the ligands coordinated to the Fe ion and is but one of the effects of the ligand field. Using the model systems [FeO(H2O)(5)](2+), representative of the weak field situation, and [FeO(H2O)(ax)(NH3)(4)](2+), representative of a strong (equatorial) field, we distinguish the effect of spin state (high spin (quintet) versus low spin (triplet)) from other effects, notably the orbital interaction (pushing up) effect of the ligand donor orbitals and the electron-donating ability of the ligands, directly affecting the charge on the FeO group. We describe the changes in electronic structure during the reaction with the help of elementary orbital interaction diagrams involving the frontier orbitals. These give a straightforward electronic structure picture of the reaction but do not provide support for the description of the reactivity of FeO2+ as starting with oxyl radical formation.

机译：（FeO2 +）-O-IV被铁离子从脂肪族CH键中夺取H的电子结构解释引起了广泛关注。我们回顾了已获得的见解，特别是对自旋状态的影响。但是，我们强调，自旋态是由与Fe离子配位的配体场决定的，而这只是配体场的作用之一。使用模型系统[FeO（H2O）（5）]（2+）表示弱磁场情况，使用[FeO（H2O）（ax）（NH3）（4）]（2+）表示强磁场情况（赤道）场，我们将自旋状态的影响（高自旋（五重态）与低自旋（三重态））与其他影响区分开来，尤其是配体供体轨道的轨道相互作用（推动）效应和电子给体能力。配体，直接影响FeO基上的电荷。我们借助涉及前沿轨道的基本轨道相互作用图描述了反应过程中电子结构的变化。这些给出了反应的简单的电子结构图，但没有为描述FeO2 +从羟基自由基开始的反应性提供支持。

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《ACS catalysis》 |2015年第3期|共14页
作者
Kazaryan Andranik; Baerends Evert Jan;
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正文语种 eng
中图分类物理化学（理论化学）、化学物理学;
关键词
nonheme iron-oxo complexes; oxidation catalysis; DFT calculations; ligand field effects; high-spin low-spin; H abstraction;

机译：非血红素铁氧配合物氧化催化DFT计算配体场效应高自旋低自旋H提取;

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1. Ligand Field Effects and the High Spin-High Reactivity Correlation in the H Abstraction by Non-Heme Iron(IV)-Oxo Complexes: A DFT Frontier Orbital Perspective [J] . Kazaryan Andranik, Baerends Evert Jan ACS catalysis . 2015,第3期

机译：非血红素铁（IV）-氧配合物在H原子提取中的配体场效应和高自旋-高反应性相关：DFT前沿轨道视角
2. DFT studies of the substituent effects of dimethylamino on non-heme active oxidizing species: iron(V)-oxo species or iron(IV)-oxo acetate aminopyridine cation radical species? [J] . Wang Fang, Sun Wei, Xia Chungu, Journal of biological inorganic chemistry: JBIC: a publication of the Society of Biological Inorganic Chemistry . 2017,第7期

机译：DFT研究二甲基氨基对非血红素活性氧化物种的研究：铁（v） - 氧化铁（IV） - 乙酸铁氨基吡啶阳离子自由基物质？
3. Water-Soluble Iron(IV)-Oxo Complexes Supported by Pentapyridine Ligands: Axial Ligand Effects on Hydrogen Atom and Oxygen Atom Transfer Reactivity [J] . Chantarojsiri Teera, Sun Yujie, Long Jeffrey R., Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics . 2015,第12期

机译：五吡啶配体支持的水溶性铁（IV）-氧配合物：轴向配体对氢原子和氧原子转移反应性的影响
4. Production, Isolation and Reactivity Studies of Metal(IV)-Oxo Species with Biomimetic Ligands: A Tandem Mass Spectrometry and Density Functional Theory Study [C] . Ivan F Taylor, Stephen J Blanksby, Stephen B Colbran, American Society for Mass Spectrometry Conference on Mass Spectrometry and Allied Topics . 2010

机译：金属（IV） - 氧化体的生产，隔离和反应性研究 - 具有仿生配体的物种：串联质谱与密度函数理论研究
5. The structure and reactivity of a series of high-valent oxo complexes of Ru and Mn: Ru(III)-mediated catalytic oxygenation of triphenylphosphine, characterization of binuclear Mn(III,III) and Mn(III,IV) dimers, and mononuclear iron(III) and iron(IV). [D] . Fackler, Nathanael L. P. 1997

机译：Ru和Mn的一系列高价羰基配合物的结构和反应性：Ru（III）介导的三苯膦催化氧化，双核Mn（III，III）和Mn（III，IV）二聚体的表征以及单核铁（III）和铁（IV）。
6. Modelling the cis-oxo-labile binding site motif of non-heme iron oxygenases. Water exchange and remarkable oxidation reactivity of a novel non-heme iron(IV)-oxo compound bearing a tripodal tetradentate ligand [O] . Dr. Anna Company, Irene Prat, Jonathan R. Frisch, -1

机译：造型非血红素氧化含量的顺式氧氧杂交粘结位点基序。新型非血红素铁（IV） - 过氧化合物的水交换和显着的氧化反应性轴承码头Tetradate配体
7. Modeling the cis-Oxo-Labile Binding Site Motif of Non-Heme Iron Oxygenases: Water Exchange and Oxidation Reactivity of a Non-Heme Iron(IV)-Oxo Compound Bearing a Tripodal Tetradentate Ligand [O] . Company Casadevall, Anna, Prat Casellas, Irene, Frisch, Jonathan R., 2011

机译：模拟非血红素铁氧合酶的顺式-不稳定氧结合位点基序：带有三脚架四齿配体的非血红素铁（IV）-氧代化合物的水交换和氧化反应性

Ligand Field Effects and the High Spin-High Reactivity Correlation in the H Abstraction by Non-Heme Iron(IV)-Oxo Complexes: A DFT Frontier Orbital Perspective

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