一种由生物启发的 N O 大环配体稳定的高反应性氧代铁(IV)配合物。
A Highly Reactive Oxoiron(IV) Complex Supported by a Bioinspired N O Macrocyclic Ligand.
机构信息
Department of Chemistry, Humboldt-Universität zu Berlin, Brook-Taylor-Strasse 2, 12489, Berlin, Germany.
Department of Chemistry and Nano Science, Ewha Womans University, Seoul, 03760, Korea.
出版信息
Angew Chem Int Ed Engl. 2017 Nov 13;56(46):14384-14388. doi: 10.1002/anie.201707872. Epub 2017 Oct 17.
Abstract
The sluggish oxidants [Fe (O)(TMC)(CH CN)] (TMC=1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) and [Fe (O)(TMCN-d )(OTf)] (TMCN-d =1,4,7,11-tetra(methyl-d )-1,4,7,11-tetraazacyclotetradecane) are transformed into the highly reactive oxidant [Fe (O)(TMCO)(OTf)] (1; TMCO=4,8,12-trimethyl-1-oxa-4,8,12-triazacyclotetradecane) upon replacement of an NMe donor in the TMC and TMCN ligands by an O atom. A rate enhancement of five to six orders of magnitude in both H atom and O atom transfer reactions was observed upon oxygen incorporation into the macrocyclic ligand. This finding was explained in terms of the higher electrophilicity of the iron center and the higher availability of the more reactive S=2 state in 1. This rationalizes nature's preference for using O-rich ligand environments for the hydroxylation of strong C-H bonds in enzymatic reactions.
摘要
sluggish 氧化剂 [Fe (O)(TMC)(CH CN)]（TMC=1,4,8,11-四甲基-1,4,8,11-四氮杂环十四烷）和 [Fe (O)(TMCN-d)(OTf)]（TMCN-d=1,4,7,11-四（甲基-d）-1,4,7,11-四氮杂环十四烷）在 TMC 和 TMCN 配体中的 NMe 供体被 O 原子取代后，转化为高反应性氧化剂 [Fe (O)(TMCO)(OTf)]（1；TMCO=4,8,12-三甲基-1-氧杂-4,8,12-三氮杂环十四烷）。在大环配体中引入氧原子后，观察到 H 原子和 O 原子转移反应的速率提高了五个到六个数量级。这一发现可以用铁中心的更高电负性和 1 中更具反应性的 S=2 态的更高可用性来解释。这就解释了自然界为什么更喜欢在酶反应中使用富氧配体环境来氧化强 C-H 键。
相似文献
1
A Highly Reactive Oxoiron(IV) Complex Supported by a Bioinspired N O Macrocyclic Ligand.一种由生物启发的 N O 大环配体稳定的高反应性氧代铁(IV)配合物。
Angew Chem Int Ed Engl. 2017 Nov 13;56(46):14384-14388. doi: 10.1002/anie.201707872. Epub 2017 Oct 17.
2
Biomimetic aryl hydroxylation derived from alkyl hydroperoxide at a nonheme iron center. Evidence for an Fe(IV)=O oxidant.在非血红素铁中心由氢过氧化烷基引发的仿生芳基羟基化反应。铁（IV）=氧氧化剂的证据。
J Am Chem Soc. 2003 Feb 26;125(8):2113-28. doi: 10.1021/ja028478l.
3
Axial ligand effects on the geometric and electronic structures of nonheme oxoiron(IV) complexes.轴向配体对非血红素氧代铁（IV）配合物的几何结构和电子结构的影响。
J Am Chem Soc. 2008 Sep 17;130(37):12394-407. doi: 10.1021/ja8022576. Epub 2008 Aug 20.
4
Intramolecular gas-phase reactions of synthetic nonheme oxoiron(IV) ions: proximity and spin-state reactivity rules.合成非血红素氧合铁(IV)离子的分子内气相反应：邻近性和自旋态反应性规则。
Chemistry. 2012 Sep 10;18(37):11747-60. doi: 10.1002/chem.201200105. Epub 2012 Jul 26.
5
Spectroscopic and Reactivity Comparisons between Nonheme Oxoiron(IV) and Oxoiron(V) Species Bearing the Same Ancillary Ligand.同配体的非血红素双氧桥铁(IV)和双氧桥铁(V)物种的光谱和反应性比较。
J Am Chem Soc. 2019 Sep 25;141(38):15078-15091. doi: 10.1021/jacs.9b05758. Epub 2019 Sep 11.
6
Oxoiron(IV) Complex of the Ethylene-Bridged Dialkylcyclam Ligand Me2EBC.乙烯桥连二烷基环胺配体Me2EBC的氧代铁（IV）配合物
Inorg Chem. 2015 Aug 17;54(16):7828-39. doi: 10.1021/acs.inorgchem.5b00861. Epub 2015 Aug 5.
7
Axial ligand tuning of a nonheme iron(IV)-oxo unit for hydrogen atom abstraction.用于氢原子提取的非血红素铁（IV）-氧单元的轴向配体调节。
Proc Natl Acad Sci U S A. 2007 Dec 4;104(49):19181-6. doi: 10.1073/pnas.0709471104. Epub 2007 Nov 28.
8
C-H Bond Cleavage by Bioinspired Nonheme Oxoiron(IV) Complexes, Including Hydroxylation of n-Butane.受生物启发的非血红素氧合铁（IV）配合物催化的C-H键裂解，包括正丁烷的羟基化反应
Inorg Chem. 2015 Jun 1;54(11):5053-64. doi: 10.1021/ic502786y. Epub 2015 Mar 9.
9
Unmasking Steps in Intramolecular Aromatic Hydroxylation by a Synthetic Nonheme Oxoiron(IV) Complex.通过合成的非血红素双氧铁(IV)配合物揭示分子内芳香羟化反应步骤。
Angew Chem Int Ed Engl. 2021 Sep 13;60(38):20991-20998. doi: 10.1002/anie.202108309. Epub 2021 Aug 11.
10
Oxygen Atom Exchange between H2O and Non-Heme Oxoiron(IV) Complexes: Ligand Dependence and Mechanism.H₂O与非血红素氧代铁（IV）配合物之间的氧原子交换：配体依赖性和机理
Inorg Chem. 2016 Jun 20;55(12):5818-27. doi: 10.1021/acs.inorgchem.6b00023. Epub 2016 Jun 8.
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
10-Fold Increase in Hydrogen Atom Transfer Reactivity for a Series of = 1 Fe═O Complexes Over the = 2 [(TQA)Fe═O] Complex via Entropic Lowering of Reaction Barriers by Secondary Sphere Cycloalkyl Substitution.通过二级球环烷基取代降低反应势垒的熵，一系列\(n = 1\)的\(Fe═O\)配合物相对于\(n = 2\)的\([(TQA)Fe═O]\)配合物的氢原子转移反应活性提高了10倍。
J Am Chem Soc. 2025 Jan 8;147(1):292-304. doi: 10.1021/jacs.4c10120. Epub 2024 Dec 19.
3
Unraveling Chlorite Oxidation Pathways in Equatorially Heteroatom-Substituted Nonheme Iron Complexes.解析赤道杂原子取代的非血红素铁配合物中的亚氯酸盐氧化途径。
ACS Org Inorg Au. 2024 Sep 20;4(6):673-680. doi: 10.1021/acsorginorgau.4c00045. eCollection 2024 Dec 4.
4
Enhanced Reactivities of Iron(IV)-Oxo Porphyrin Species in Oxidation Reactions Promoted by Intramolecular Hydrogen-Bonding.分子内氢键促进的氧化反应中铁（IV）-氧代卟啉物种的反应活性增强
Adv Sci (Weinh). 2024 May;11(19):e2310333. doi: 10.1002/advs.202310333. Epub 2024 Mar 13.
5
Characterization of a Ferryl Flip in Electronically Tuned Nonheme Complexes. Consequences in Hydrogen Atom Transfer Reactivity.电子调谐非血红素配合物中 Ferryl Flip 的特性。对氢原子转移反应性的影响。
Angew Chem Int Ed Engl. 2023 Jan 9;62(2):e202211361. doi: 10.1002/anie.202211361. Epub 2022 Dec 2.
6
Heme compound II models in chemoselectivity and disproportionation reactions.化学选择性和歧化反应中的血红素化合物II模型
Chem Sci. 2022 Apr 12;13(19):5707-5717. doi: 10.1039/d2sc01232d. eCollection 2022 May 18.
7
New Strategies for Direct Methane-to-Methanol Conversion from Active Learning Exploration of 16 Million Catalysts.通过对1600万种催化剂的主动学习探索实现直接甲烷制甲醇转化的新策略
JACS Au. 2022 Apr 27;2(5):1200-1213. doi: 10.1021/jacsau.2c00176. eCollection 2022 May 23.
8
Nonheme Diiron Oxygenase Mimic That Generates a Diferric-Peroxo Intermediate Capable of Catalytic Olefin Epoxidation and Alkane Hydroxylation Including Cyclohexane.非血红素双铁加氧酶模拟物，可生成一种双铁-过氧中间体，能够催化烯烃环氧化和烷烃羟基化反应，包括环己烷的羟基化反应。
Inorg Chem. 2022 Jan 10;61(1):37-41. doi: 10.1021/acs.inorgchem.1c03468. Epub 2021 Dec 11.
9
C-H Bond Cleavage by Bioinspired Nonheme Metal Complexes.生物启发的非血红素金属配合物的 C-H 键断裂。
Inorg Chem. 2021 Sep 20;60(18):13759-13783. doi: 10.1021/acs.inorgchem.1c01754. Epub 2021 Sep 7.
10
Semiempirical method for examining asynchronicity in metal-oxido-mediated C-H bond activation.考察金属-氧介导的 C-H 键活化中异步性的半经验方法。
Proc Natl Acad Sci U S A. 2021 Sep 7;118(36). doi: 10.1073/pnas.2108648118.
本文引用的文献
1
Structure and spin state of nonheme FeO complexes depending on temperature: predictive insights from DFT calculations and experiments.非血红素FeO配合物的结构和自旋状态随温度的变化：来自密度泛函理论计算和实验的预测性见解。
Chem Sci. 2017 Aug 1;8(8):5460-5467. doi: 10.1039/c7sc01738c. Epub 2017 May 30.
2
Nonclassical Single-State Reactivity of an Oxo-Iron(IV) Complex Confined to Triplet Pathways.限域于三重态通道的双氧-铁(IV)配合物的非经典单态反应性。
J Am Chem Soc. 2017 Jul 5;139(26):8939-8949. doi: 10.1021/jacs.7b03255. Epub 2017 Jun 22.
3
Magnetic Circular Dichroism Evidence for an Unusual Electronic Structure of a Tetracarbene-Oxoiron(IV) Complex.磁圆二色性证据表明四碳烯-氧代铁(IV)配合物具有不寻常的电子结构。
J Am Chem Soc. 2016 Nov 2;138(43):14312-14325. doi: 10.1021/jacs.6b07708. Epub 2016 Oct 21.
4
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.
5
Toward the synthesis of more reactive S = 2 non-heme oxoiron(IV) complexes.迈向更具反应性的 S = 2 非血红素氧代铁（IV）配合物的合成。
Acc Chem Res. 2015 Aug 18;48(8):2443-52. doi: 10.1021/acs.accounts.5b00244. Epub 2015 Jul 15.
6
Modeling TauD-J: a high-spin nonheme oxoiron(IV) complex with high reactivity toward C-H bonds.构建 TauD-J：一种具有高自旋的非血红素双氧桥铁（IV）配合物，对 C-H 键具有高反应活性。
J Am Chem Soc. 2015 Feb 25;137(7):2428-31. doi: 10.1021/ja511757j. Epub 2015 Feb 17.
7
Status of reactive non-heme metal-oxygen intermediates in chemical and enzymatic reactions.化学反应和酶反应中活性非血红素金属-氧中间体的状态。
J Am Chem Soc. 2014 Oct 8;136(40):13942-58. doi: 10.1021/ja507807v. Epub 2014 Sep 29.
8
Oxidation of ethane to ethanol by N2O in a metal-organic framework with coordinatively unsaturated iron(II) sites.在具有配位不饱和铁(II)位点的金属有机骨架中用 N2O 将乙烷氧化为乙醇。
Nat Chem. 2014 Jul;6(7):590-5. doi: 10.1038/nchem.1956. Epub 2014 May 18.
9
Reactivity comparison of high-valent iron(IV)-oxo complexes bearing N-tetramethylated cyclam ligands with different ring size.大环配体 N-四甲基环戊二烯基甲胺配合的高价态铁(IV)-氧配合物的反应活性比较。
Dalton Trans. 2013 Jun 14;42(22):7842-5. doi: 10.1039/c3dt50750e. Epub 2013 Apr 16.
10
A Mononuclear Carboxylate-Rich Oxoiron(IV) Complex: a Structural and Functional Mimic of TauD Intermediate 'J'.一种富含单核羧酸盐的氧代铁（IV）配合物：TauD中间体“J”的结构和功能模拟物
Chem Sci. 2012;3:1680-1693. doi: 10.1039/C2SC01044E. Epub 2012 Feb 20.
Zotero 插件