Ce 3+ 和 HClO 促进室温下 Fe = O 单体前体组装成 Fe（μ-O）金刚石核。
Ce - and HClO -Promoted Assembly of an Fe (μ-O) Diamond Core from its Monomeric Fe =O Precursor at Room Temperature.
机构信息
Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, Minneapolis, Minnesota, 55455, USA.
Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, 208016, India.
出版信息
Angew Chem Int Ed Engl. 2020 Dec 7;59(50):22484-22488. doi: 10.1002/anie.202010027. Epub 2020 Oct 6.
Abstract
Diiron(IV)-oxo species are proposed to effect the cleavage of strong C-H bonds by nonheme diiron enzymes such as soluble methane monooxygenase (sMMO) and fatty acid desaturases. However, synthetic mimics of such diiron(IV) oxidants are rare. Herein we report the reaction of (TPA*)Fe (1) (TPA*=tris(3,5-dimethyl-4-methoxypyridyl-2-methyl)amine) in CH CN with 4 equiv CAN and 200 equiv HClO at 20 °C to form a complex with an [Fe (μ-O) ] core. CAN and HClO play essential roles in this unprecedented transformation, in which the comproportionation of Fe -O-Ce and Fe =O/Ce species is proposed to be involved in the assembly of the [Fe (μ-O) ] core.
摘要
二价铁（IV）-氧物种被认为可以通过非血红素二铁酶（如可溶性甲烷单加氧酶（sMMO）和脂肪酸去饱和酶）来断裂强 C-H 键。然而，这种二价铁（IV）氧化剂的合成模拟物很少。在此，我们报告了在 20°C 下，（TPA*）Fe（1）（TPA*=三（3,5-二甲基-4-甲氧基-2-甲基）吡啶-2-甲基）在 CH 3 CN 中与 4 当量的 CAN 和 200 当量的 HClO 反应，形成具有[Fe（μ-O）]核心的配合物。CAN 和 HClO 在这个前所未有的转化中起着至关重要的作用，其中 Fe-O-Ce 和 Fe=O/Ce 物种的等价体被认为参与了[Fe（μ-O）]核心的组装。
相似文献
1
Ce - and HClO -Promoted Assembly of an Fe (μ-O) Diamond Core from its Monomeric Fe =O Precursor at Room Temperature.Ce 3+ 和 HClO 促进室温下 Fe = O 单体前体组装成 Fe（μ-O）金刚石核。
Angew Chem Int Ed Engl. 2020 Dec 7;59(50):22484-22488. doi: 10.1002/anie.202010027. Epub 2020 Oct 6.
2
Substrate-triggered activation of a synthetic [Fe2(μ-O)2] diamond core for C-H bond cleavage.底物触发的用于 C-H 键断裂的合成 [Fe2(μ-O)2] 金刚石核的激活。
J Am Chem Soc. 2011 Oct 19;133(41):16657-67. doi: 10.1021/ja207131g. Epub 2011 Sep 21.
3
Mössbauer and DFT study of the ferromagnetically coupled diiron(IV) precursor to a complex with an Fe(IV)(2)O(2) diamond core.具有Fe(IV)₂O₂菱形核心的配合物的铁磁耦合二价铁(IV)前体的穆斯堡尔谱和密度泛函理论研究
J Am Chem Soc. 2009 Apr 29;131(16):5823-30. doi: 10.1021/ja8098917.
4
Evaluating the identity and diiron core transformations of a (μ-oxo)diiron(III) complex supported by electron-rich tris(pyridyl-2-methyl)amine ligands.评估由富电子三（吡啶-2-甲基）胺配体支持的（μ-氧）双核铁（III）配合物的身份和双核铁核心转化。
Inorg Chem. 2012 Feb 20;51(4):2393-402. doi: 10.1021/ic202379b. Epub 2012 Jan 20.
5
Brønsted acid-promoted C-H bond cleavage via electron transfer from toluene derivatives to a protonated nonheme iron(IV)-oxo complex with no kinetic isotope effect.布朗斯特酸促进的 C-H 键断裂，通过甲苯衍生物向质子化的非血红素铁(IV)-氧络合物进行电子转移，没有动力学同位素效应。
J Am Chem Soc. 2013 Apr 3;135(13):5052-61. doi: 10.1021/ja311662w. Epub 2013 Mar 25.
6
Sc-Promoted O-O Bond Cleavage of a (μ-1,2-Peroxo)diiron(III) Species Formed from an Iron(II) Precursor and O to Generate a Complex with an Fe(μ-O) Core.Sc 促进的 (μ-1,2-过氧)二铁(III)物种中 O-O 键断裂，该物种由铁(II)前体和 O 形成，生成具有 Fe(μ-O)核的配合物。
J Am Chem Soc. 2020 Mar 4;142(9):4285-4297. doi: 10.1021/jacs.9b12081. Epub 2020 Feb 19.
7
Highly Reactive Co(μ-O) Diamond Core Complex That Cleaves C-H Bonds.高反应性 Co(μ-O) 二聚体核心复合物可切断 C-H 键。
J Am Chem Soc. 2019 Dec 26;141(51):20127-20136. doi: 10.1021/jacs.9b09531. Epub 2019 Dec 16.
8
Interplay of Electronic Cooperativity and Exchange Coupling in Regulating the Reactivity of Diiron(IV)-oxo Complexes towards C-H and O-H Bond Activation.电子协同作用与交换耦合在调节二铁（IV）-氧配合物对C-H和O-H键活化反应性中的相互作用
Chemistry. 2017 Jul 26;23(42):10110-10125. doi: 10.1002/chem.201701059. Epub 2017 Jul 5.
9
An abiotic analogue of the diiron(IV)oxo "diamond core" of soluble methane monooxygenase generated by direct activation of O2 in aqueous Fe(II)/EDTA solutions: thermodynamics and electronic structure.在含有 Fe(II)和 EDTA 的水溶液中直接激活 O2 生成的可溶性甲烷单加氧酶中二价铁(IV)氧“金刚石核”的非生物类似物：热力学和电子结构。
Phys Chem Chem Phys. 2011 Sep 7;13(33):15272-82. doi: 10.1039/c1cp21244c. Epub 2011 Jul 21.
10
Substrate-dependent H/D kinetic isotope effects and the role of the di(μ-oxo)diiron(IV) core in soluble methane monooxygenase: a theoretical study.底物依赖性氢/氘动力学同位素效应及双（μ-氧代）二铁（IV）核心在可溶性甲烷单加氧酶中的作用：一项理论研究
Chemistry. 2014 May 19;20(21):6532-41. doi: 10.1002/chem.201303466. Epub 2014 Apr 8.
引用本文的文献
1
Formation of a Mn-O-Ce species from a Mn-hydroxo complex and ceric ammonium nitrate.由锰羟基络合物和硝酸铈铵形成锰-氧-铈物种。
Dalton Trans. 2025 Sep 1. doi: 10.1039/d5dt01728a.
2
Formation of a Reactive [Mn(III)-O-Ce(IV)] Species and its Facile Equilibrium with Related Mn(IV)(OX) (X = Sc or H) Complexes.活性[Mn(III)-O-Ce(IV)]物种的形成及其与相关Mn(IV)(OX)（X = Sc或H）配合物的易位平衡。
Angew Chem Int Ed Engl. 2024 Jan 15;63(3):e202316378. doi: 10.1002/anie.202316378. Epub 2023 Dec 7.
本文引用的文献
1
Sc-Promoted O-O Bond Cleavage of a (μ-1,2-Peroxo)diiron(III) Species Formed from an Iron(II) Precursor and O to Generate a Complex with an Fe(μ-O) Core.Sc 促进的 (μ-1,2-过氧)二铁(III)物种中 O-O 键断裂，该物种由铁(II)前体和 O 形成，生成具有 Fe(μ-O)核的配合物。
J Am Chem Soc. 2020 Mar 4;142(9):4285-4297. doi: 10.1021/jacs.9b12081. Epub 2020 Feb 19.
2
A High-Valent Manganese(IV)-Oxo-Cerium(IV) Complex and Its Enhanced Oxidizing Reactivity.高价态锰(IV)-氧-铈(IV)配合物及其增强的氧化反应活性。
Angew Chem Int Ed Engl. 2019 Nov 4;58(45):16124-16129. doi: 10.1002/anie.201910032. Epub 2019 Sep 24.
3
Soluble Methane Monooxygenase.可溶性甲烷单加氧酶。
Annu Rev Biochem. 2019 Jun 20;88:409-431. doi: 10.1146/annurev-biochem-013118-111529. Epub 2019 Jan 11.
4
High-Resolution Extended X-ray Absorption Fine Structure Analysis Provides Evidence for a Longer Fe···Fe Distance in the Q Intermediate of Methane Monooxygenase.高分辨率扩展 X 射线吸收精细结构分析为甲烷单加氧酶 Q 中间物中 Fe···Fe 距离更长提供了证据。
J Am Chem Soc. 2018 Dec 5;140(48):16807-16820. doi: 10.1021/jacs.8b10313. Epub 2018 Nov 16.
5
Dioxygen Activation by Nonheme Diiron Enzymes: Diverse Dioxygen Adducts, High-Valent Intermediates, and Related Model Complexes.非血红素二铁酶的分子氧活化：多样的双氧加合物、高价态中间体和相关模型配合物。
Chem Rev. 2018 Mar 14;118(5):2554-2592. doi: 10.1021/acs.chemrev.7b00457. Epub 2018 Feb 5.
6
High-Energy-Resolution Fluorescence-Detected X-ray Absorption of the Q Intermediate of Soluble Methane Monooxygenase.可溶性甲烷单加氧酶 Q 中间态的高能量分辨率荧光探测 X 射线吸收。
J Am Chem Soc. 2017 Dec 13;139(49):18024-18033. doi: 10.1021/jacs.7b09560. Epub 2017 Dec 1.
7
Facile and Reversible Formation of Iron(III)-Oxo-Cerium(IV) Adducts from Nonheme Oxoiron(IV) Complexes and Cerium(III).非血红素氧合铁(IV)配合物与铈(III)制备铁(III)-氧-铈(IV)加合物的简便和可逆方法。
Angew Chem Int Ed Engl. 2017 Jul 24;56(31):9091-9095. doi: 10.1002/anie.201704322. Epub 2017 Jun 27.
8
Spectroscopic and Reactivity Comparisons of a Pair of bTAML Complexes with Fe═O and Fe═O Units.一对具有Fe═O和Fe═O单元的bTAML配合物的光谱和反应性比较
Inorg Chem. 2017 Jun 5;56(11):6352-6361. doi: 10.1021/acs.inorgchem.7b00448. Epub 2017 May 8.
9
X-ray structure of a mammalian stearoyl-CoA desaturase.一种哺乳动物硬脂酰辅酶A去饱和酶的X射线结构。
Nature. 2015 Aug 13;524(7564):252-6. doi: 10.1038/nature14549. Epub 2015 Jun 22.
10
Evidence for an oxygen evolving iron-oxo-cerium intermediate in iron-catalysed water oxidation.铁催化水氧化过程中氧析出铁-氧-铈中间体的证据。
Nat Commun. 2015 Jan 22;6:5865. doi: 10.1038/ncomms6865.
Zotero 插件