实现单核非血红素铁(V)-亚胺单电子氧化。
Achieving One-Electron Oxidation of a Mononuclear Nonheme Iron(V)-Imido Complex.
机构信息
Department of Chemistry and Nano Science, Ewha Womans University , Seoul 03760, Korea.
Department of Chemistry, Sookmyung Women's University , Seoul 04310, Korea.
出版信息
J Am Chem Soc. 2017 Oct 18;139(41):14372-14375. doi: 10.1021/jacs.7b08161. Epub 2017 Oct 4.
Abstract
A mononuclear nonheme iron(V)-imido complex bearing a tetraamido macrocyclic ligand (TAML), [Fe(NTs)(TAML)] (1), was oxidized by one-electron oxidants, affording formation of an iron(V)-imido TAML cation radical species, [Fe(NTs)(TAML)] (2); 2 is a diamagnetic (S = 0) complex, resulting from the antiferromagnetic coupling of the low-spin iron(V) ion (S = 1/2) with the one-electron oxidized ligand (TAML). 2 is a competent oxidant in C-H bond functionalization and nitrene transfer reaction, showing that the reactivity of 2 is greater than that of 1.
摘要
单核非血红素铁（V）-亚胺配合物带有一个四氨大环配体（TAML），[Fe（NTs）（TAML）]（1），被单电子氧化剂氧化，形成铁（V）-亚胺 TAML 阳离子自由基物种，[Fe（NTs）（TAML）]（2）；2 是一个抗磁性（S = 0）的配合物，这是由于低自旋铁（V）离子（S = 1/2）与单电子氧化配体（TAML）之间的反铁磁耦合所致。2 是 C-H 键官能化和氮烯转移反应的有效氧化剂，表明 2 的反应性大于 1。
相似文献
1
Achieving One-Electron Oxidation of a Mononuclear Nonheme Iron(V)-Imido Complex.实现单核非血红素铁(V)-亚胺单电子氧化。
J Am Chem Soc. 2017 Oct 18;139(41):14372-14375. doi: 10.1021/jacs.7b08161. Epub 2017 Oct 4.
2
A Mononuclear Nonheme Iron(V)-Imido Complex.单核非血红素铁(V)-亚胺配合物。
J Am Chem Soc. 2017 Jul 5;139(26):8800-8803. doi: 10.1021/jacs.7b04695. Epub 2017 Jun 23.
3
Electron-Transfer and Redox Reactivity of High-Valent Iron Imido and Oxo Complexes with the Formal Oxidation States of Five and Six.高价态铁亚胺和氧代配合物的电子转移和氧化还原反应，其形式氧化态分别为五价和六价。
J Am Chem Soc. 2020 Feb 26;142(8):3891-3904. doi: 10.1021/jacs.9b11682. Epub 2020 Feb 18.
4
Nonheme Iron Imido Complexes Bearing a Non-Innocent Ligand: A Synthetic Chameleon Species in Oxidation Reactions.非血红素铁亚氨配合物负载非惰性配体：氧化反应中的一种合成变色龙物种。
Chemistry. 2021 Dec 9;27(69):17495-17503. doi: 10.1002/chem.202103295. Epub 2021 Oct 25.
5
Synthetic mononuclear nonheme iron-oxygen intermediates.合成单核非血红素铁-氧中间体。
Acc Chem Res. 2015 Aug 18;48(8):2415-23. doi: 10.1021/acs.accounts.5b00218. Epub 2015 Jul 23.
6
A Mononuclear Nonheme Iron(IV)-Amido Complex Relevant for the Compound II Chemistry of Cytochrome P450.与细胞色素 P450 的复合 II 化学有关的单核非血红素铁（IV）-酰胺配合物。
J Am Chem Soc. 2019 Jan 9;141(1):80-83. doi: 10.1021/jacs.8b11045. Epub 2018 Dec 20.
7
Catalytic C-H bond amination from high-spin iron imido complexes.高自旋铁亚胺配合物的催化 C-H 键胺化反应。
J Am Chem Soc. 2011 Apr 6;133(13):4917-23. doi: 10.1021/ja110066j. Epub 2011 Mar 15.
8
Tuning reactivity and mechanism in oxidation reactions by mononuclear nonheme iron(IV)-oxo complexes.通过单核非血红素铁(IV)-氧配合物来调节氧化反应的反应活性和反应机理。
Acc Chem Res. 2014 Apr 15;47(4):1146-54. doi: 10.1021/ar400258p. Epub 2014 Feb 13.
9
Mechanistic Insight into the Nitric Oxide Dioxygenation Reaction of Nonheme Iron(III)-Superoxo and Manganese(IV)-Peroxo Complexes.非血红素铁（III）-超氧和锰（IV）-过氧配合物的一氧化氮双氧反应的机理见解。
Angew Chem Int Ed Engl. 2016 Sep 26;55(40):12403-7. doi: 10.1002/anie.201605705. Epub 2016 Sep 4.
10
A Manganese(V)-Oxo Tetraamido Macrocyclic Ligand (TAML) Cation Radical Complex: Synthesis, Characterization, and Reactivity Studies.锰(V)-氧四氨大环配体（TAML）阳离子自由基配合物的合成、表征及反应性研究。
Chemistry. 2018 Dec 5;24(68):17927-17931. doi: 10.1002/chem.201804898. Epub 2018 Nov 19.
引用本文的文献
1
Preparation, Spectroscopic Characterization, and Reactivity of High-Valent Non-Oxo Co(IV) and Formally Co(V) Complexes.高价非氧合钴（IV）和形式上的钴（V）配合物的制备、光谱表征及反应活性
JACS Au. 2025 Jul 15;5(7):3575-3588. doi: 10.1021/jacsau.5c00589. eCollection 2025 Jul 28.
2
A Mechanistic Study on Iron-Based Styrene Aziridination: Understanding Epoxidation via Nitrene Hydrolysis.铁基苯乙烯氮杂环丙烷化的机理研究：通过氮烯水解理解环氧化反应
Molecules. 2024 Jul 24;29(15):3470. doi: 10.3390/molecules29153470.
3
Ruthenium(v) terminal arylimido corroles: isolation, spectroscopic characterization and reactivity.钌（Ⅴ）末端芳基亚胺基咕啉：分离、光谱表征及反应活性
Chem Sci. 2023 Sep 2;14(38):10602-10609. doi: 10.1039/d3sc02266h. eCollection 2023 Oct 4.
4
Spin polarization assisted facile C-H activation by an = 1 iron(iv)-bisimido complex: a comprehensive spectroscopic and theoretical investigation.自旋极化辅助的由一个S = 1的双亚胺铁（IV）配合物实现的简便C-H活化：一项全面的光谱和理论研究。
Chem Sci. 2023 Feb 15;14(11):2808-2820. doi: 10.1039/d2sc06273a. eCollection 2023 Mar 15.
5
Electronically Asynchronous Transition States for C-N Bond Formation by Electrophilic -Nitrene Radical Complexes Involving Substrate-to-Ligand Single-Electron Transfer and a Cobalt-Centered Spin Shuttle.通过涉及底物到配体单电子转移和钴中心自旋穿梭的亲电氮自由基配合物形成C-N键的电子异步过渡态。
ACS Catal. 2020 Jul 17;10(14):7449-7463. doi: 10.1021/acscatal.0c01343. Epub 2020 Jun 12.
6
Rational design of iron catalysts for C-X bond activation.铁催化剂的 C-X 键活化的合理设计。
J Comput Chem. 2023 Feb 5;44(4):495-505. doi: 10.1002/jcc.26818. Epub 2022 Feb 8.
7
A Combined Spectroscopic and Computational Study on the Mechanism of Iron-Catalyzed Aminofunctionalization of Olefins Using Hydroxylamine Derived N-O Reagent as the "Amino" Source and "Oxidant".铁催化烯烃的氨官能化反应机理的光谱和计算联合研究：以羟胺衍生的 N-O 试剂作为“氨基”源和“氧化剂”。
J Am Chem Soc. 2022 Feb 16;144(6):2637-2656. doi: 10.1021/jacs.1c11083. Epub 2022 Feb 4.
8
A Pair of Cobalt(III/IV) Terminal Imido Complexes.一对钴（III/IV）端亚胺配合物。
Angew Chem Int Ed Engl. 2021 Jul 19;60(30):16480-16486. doi: 10.1002/anie.202103170. Epub 2021 Jun 18.
9
Catalytic Chemoselective Sulfimidation with an Electrophilic [Co (TAML)] -Nitrene Radical Complex*.亲电[钴（TAML）]-氮烯自由基配合物的催化化学选择性亚磺酰化*
Chemistry. 2021 Jan 4;27(1):371-378. doi: 10.1002/chem.202003566. Epub 2020 Nov 19.
10
Octahedral iron(iv)-tosylimido complexes exhibiting single electron-oxidation reactivity.具有单电子氧化反应活性的八面体铁（IV）-对甲苯磺酰亚胺配合物。
Chem Sci. 2019 Aug 20;10(41):9513-9529. doi: 10.1039/c9sc02526j. eCollection 2019 Nov 7.
本文引用的文献
1
A Mononuclear Nonheme Iron(V)-Imido Complex.单核非血红素铁(V)-亚胺配合物。
J Am Chem Soc. 2017 Jul 5;139(26):8800-8803. doi: 10.1021/jacs.7b04695. Epub 2017 Jun 23.
2
Spectroscopic and Computational Studies of Spin States of Iron(IV) Nitrido and Imido Complexes.铁（IV）氮化物和亚胺配合物自旋态的光谱和计算研究。
Inorg Chem. 2017 Apr 17;56(8):4752-4769. doi: 10.1021/acs.inorgchem.7b00512. Epub 2017 Apr 5.
3
Redox Self-Adaptation of a Nitrene Transfer Catalyst to the Substrate Needs.氧化还原自适应氮烯转移催化剂对底物需求。
Angew Chem Int Ed Engl. 2017 Apr 3;56(15):4305-4309. doi: 10.1002/anie.201612472. Epub 2017 Mar 15.
4
A new look at the role of thiolate ligation in cytochrome P450.硫醇盐连接在细胞色素P450中的作用新视角。
J Biol Inorg Chem. 2017 Apr;22(2-3):209-220. doi: 10.1007/s00775-016-1430-3. Epub 2017 Jan 16.
5
Beyond ferryl-mediated hydroxylation: 40 years of the rebound mechanism and C-H activation.超越铁（IV）介导的羟基化作用：40年的反弹机制与C-H活化
J Biol Inorg Chem. 2017 Apr;22(2-3):185-207. doi: 10.1007/s00775-016-1414-3. Epub 2016 Dec 1.
6
Spectroscopic analyses of 2-oxoglutarate-dependent oxygenases: TauD as a case study.2-酮戊二酸依赖性加氧酶的光谱分析：以TauD为例
J Biol Inorg Chem. 2017 Apr;22(2-3):367-379. doi: 10.1007/s00775-016-1406-3. Epub 2016 Nov 3.
7
O Activation by Non-Heme Iron Enzymes.非血红素铁酶的激活作用。
Biochemistry. 2016 Nov 22;55(46):6363-6374. doi: 10.1021/acs.biochem.6b00635. Epub 2016 Nov 14.
8
Oxidation Reactions with Bioinspired Mononuclear Non-Heme Metal-Oxo Complexes.单核非血红素金属-氧配合物的仿生氧化反应。
Angew Chem Int Ed Engl. 2016 Jun 27;55(27):7632-49. doi: 10.1002/anie.201600507. Epub 2016 Jun 16.
9
Characterization of Iron-Imido Species Relevant for N-Group Transfer Chemistry.与N-基团转移化学相关的铁-亚胺物种的表征
J Am Chem Soc. 2016 Feb 17;138(6):1983-93. doi: 10.1021/jacs.5b12582. Epub 2016 Feb 4.
10
Three-coordinate iron(IV) bisimido complexes with aminocarbene ligation: synthesis, structure, and reactivity.三坐标铁(IV)双亚胺配合物与氨基卡宾键合：合成、结构和反应性。
J Am Chem Soc. 2015 Nov 11;137(44):14196-207. doi: 10.1021/jacs.5b09579. Epub 2015 Oct 27.
Zotero 插件