氢氧根和甲醇根配体对铁卟啉高价态的稳定作用：铁（IV）-氧卟啉的电化学生成
Stabilization of higher-valent states of iron porphyrin by hydroxide and methoxide ligands: electrochemical generation of iron(IV)-oxo porphyrins.
作者信息
Lee W A, Calderwood T S, Bruice T C
出版信息
Proc Natl Acad Sci U S A. 1985 Jul;82(13):4301-5. doi: 10.1073/pnas.82.13.4301.
Abstract
An electrochemical study of hydroxide- and methoxide-ligated iron(III) tetraphenylporphyrins possessing ortho-phenyl substituents that block mu-oxo dimer formation has been carried out. Ligation by these strongly basic oxyanions promotes the formation of iron(IV)-oxo porphyrins upon one-electron oxidation. Further one-electron oxidation of the latter provides the iron(IV)-oxo porphyrin pi-cation radical. These results are discussed in terms of chemical model studies and the enzymatic intermediate compounds I and II of the peroxidases.
摘要
对具有邻位苯基取代基以阻止μ-氧二聚体形成的氢氧化物和甲醇盐配位的铁(III)四苯基卟啉进行了电化学研究。这些强碱性氧阴离子的配位作用促进了单电子氧化时铁(IV)-氧卟啉的形成。后者进一步的单电子氧化产生铁(IV)-氧卟啉π-阳离子自由基。根据化学模型研究以及过氧化物酶的酶促中间体化合物I和II对这些结果进行了讨论。
相似文献
1
Stabilization of higher-valent states of iron porphyrin by hydroxide and methoxide ligands: electrochemical generation of iron(IV)-oxo porphyrins.氢氧根和甲醇根配体对铁卟啉高价态的稳定作用：铁（IV）-氧卟啉的电化学生成
Proc Natl Acad Sci U S A. 1985 Jul;82(13):4301-5. doi: 10.1073/pnas.82.13.4301.
2
Mechanistic insight into formation of oxo-iron(IV) porphyrin pi-cation radicals from enzyme mimics of cytochrome P450 in organic solvents.关于在有机溶剂中由细胞色素P450酶模拟物形成氧代铁（IV）卟啉π-阳离子自由基的机理洞察。
Chemistry. 2009;15(12):2941-59. doi: 10.1002/chem.200801423.
3
Valence-tautomerism in high-valent iron and manganese porphyrins.高价铁和锰卟啉中的价互变异构现象。
J Biol Inorg Chem. 2001 Oct;6(8):831-45. doi: 10.1007/s007750100277.
4
Enhanced reactivities of iron(IV)-oxo porphyrin pi-cation radicals in oxygenation reactions by electron-donating axial ligands.电子给体轴向配体增强铁(IV)-氧代卟啉π-阳离子自由基在氧合反应中的反应活性。
Chemistry. 2009 Oct 5;15(39):10039-46. doi: 10.1002/chem.200901238.
5
Effect of the axial ligand on substrate sulfoxidation mediated by iron(IV)-oxo porphyrin cation radical oxidants.轴向配体对铁(IV)-氧代卟啉阳离子自由基氧化剂介导的底物氧化的影响。
Chemistry. 2011 May 23;17(22):6196-205. doi: 10.1002/chem.201003187. Epub 2011 Apr 5.
6
Direct evidence for an iron(IV)-oxo porphyrin pi-cation radical as an active oxidant in catalytic oxygenation reactions.铁（IV）-氧代卟啉π-阳离子自由基作为催化氧化反应中的活性氧化剂的直接证据。
Chem Commun (Camb). 2008 Mar 7(9):1076-8. doi: 10.1039/b716558g. Epub 2008 Jan 3.
7
High-valent iron(IV)-oxo complexes of heme and non-heme ligands in oxygenation reactions.血红素和非血红素配体的高价铁（IV）-氧络合物在氧化反应中的作用。
Acc Chem Res. 2007 Jul;40(7):522-31. doi: 10.1021/ar700027f. Epub 2007 May 1.
8
Significant Electronic Effect of Porphyrin Ligand on the Reactivities of High-Valent Iron(IV) Oxo Porphyrin Cation Radical Complexes.卟啉配体对高价铁（IV）氧卟啉阳离子自由基配合物反应活性的显著电子效应
Inorg Chem. 1999 Mar 8;38(5):914-920. doi: 10.1021/ic980989e.
9
Mechanistic studies on peroxide activation by a water-soluble iron(III)-porphyrin: implications for O-O bond activation in aqueous and nonaqueous solvents.水溶性铁（III）-卟啉对过氧化物活化的机理研究：对水相和非水相溶剂中O-O键活化的启示
Chemistry. 2007;13(17):4873-83. doi: 10.1002/chem.200601148.
10
Insights from kinetic studies of photo-generated compound II models: Reactivity toward aryl sulfides.光致化合物 II 模型的动力学研究的新见解：对芳基硫醚的反应性。
J Inorg Biochem. 2018 Jun;183:58-65. doi: 10.1016/j.jinorgbio.2018.03.004. Epub 2018 Mar 9.
引用本文的文献
1
Intricacies of Mass Transport during Electrocatalysis: A Journey through Iron Porphyrin-Catalyzed Oxygen Reduction.电催化过程中传质的复杂性：铁卟啉催化氧还原的探索之旅
J Am Chem Soc. 2024 Jun 5;146(22):15619-15626. doi: 10.1021/jacs.4c04989. Epub 2024 May 23.
2
Microbial biofilms as living photoconductors due to ultrafast electron transfer in cytochrome OmcS nanowires.微生物生物膜作为活体光导体，由于细胞色素 OmcS 纳米线中的超快电子转移。
Nat Commun. 2022 Sep 7;13(1):5150. doi: 10.1038/s41467-022-32659-5.
3
Oxoiron(v) mediated selective electrochemical oxygenation of unactivated C-H and C[double bond, length as m-dash]C bonds using water as the oxygen source.以水为氧源，通过氧代铁（Ⅴ）介导实现未活化C-H键和C═C键的选择性电化学氧化。
Chem Sci. 2020 Sep 24;11(43):11877-11885. doi: 10.1039/d0sc03616a.
4
Electrochemical C-H oxygenation and alcohol dehydrogenation involving Fe-oxo species using water as the oxygen source.使用水作为氧源，涉及铁氧物种的电化学C-H氧化和醇脱氢反应。
Chem Sci. 2019 Jun 27;10(32):7542-7548. doi: 10.1039/c9sc02609f. eCollection 2019 Aug 28.
5
Feasibility of Performing Concurrent Coulometric Titrations Using a Multicompartment Electrolysis Cell.使用多隔室电解池进行同时库仑滴定的可行性。
ACS Omega. 2019 Feb 19;4(2):3684-3689. doi: 10.1021/acsomega.8b03141. eCollection 2019 Feb 28.
6
Synthetic Fe/Cu Complexes: Toward Understanding Heme-Copper Oxidase Structure and Function.合成 Fe/Cu 配合物：深入了解血红素铜氧化酶的结构与功能。
Chem Rev. 2018 Nov 28;118(22):10840-11022. doi: 10.1021/acs.chemrev.8b00074. Epub 2018 Oct 29.
7
Ground State and Excited State Tuning in Ferric Dipyrrin Complexes Promoted by Ancillary Ligand Exchange.辅助配体交换促进的二吡咯铁配合物的基态和激发态调控
Inorg Chem. 2017 May 15;56(10):5892-5901. doi: 10.1021/acs.inorgchem.7b00525. Epub 2017 Apr 24.
8
Dynamics of Radical Intermediates in Prostaglandin H Synthase-1 Cyclooxygenase Reactions is Modulated by Multiple Factors.前列腺素H合酶-1环氧化酶反应中自由基中间体的动力学受多种因素调控。
Protein Pept Lett. 2016;23(11):1013-1023. doi: 10.2174/0929866523666161007151812.
9
Kinetics and mechanism of oxidation reactions of porphyrin-iron(IV)-oxo intermediates.卟啉-铁（IV）-氧中间体的氧化反应动力学及机理
Inorg Chem. 2007 Aug 6;46(16):6767-74. doi: 10.1021/ic700395j. Epub 2007 Jul 14.
10
electrochemical generation of a nonheme oxoiron(IV) complex.非血红素氧代铁（IV）配合物的电化学生成
Inorg Chem. 2006 Oct 2;45(20):8009-11. doi: 10.1021/ic061263i.
本文引用的文献
1
Electron-nuclear double resonance of horseradish peroxidase compound I. Detection of the porphyrin pi-cation radical.辣根过氧化物酶化合物I的电子-核双共振。卟啉π-阳离子自由基的检测。
J Biol Chem. 1981 Mar 10;256(5):2118-21.
2
Mössbauer spectroscopic evidence for the electronic configuration of iron in horseradish peroxidase and its peroxide derivatives.
Biochemistry. 1969 Oct;8(10):4159-62. doi: 10.1021/bi00838a037.
3
Compounds I of catalase and horse radish peroxidase: pi-cation radicals.过氧化氢酶和辣根过氧化物酶的化合物I：π-阳离子自由基。
Proc Natl Acad Sci U S A. 1971 Mar;68(3):614-8. doi: 10.1073/pnas.68.3.614.
4
Iron(IV) porphyrins.铁（IV）卟啉
J Am Chem Soc. 1971 Nov;93(23):6332-4. doi: 10.1021/ja00752a091.
5
Interaction of peroxidases with aromatic peracids and alkyl peroxides. Product analysis.过氧化物酶与芳族过酸和烷基过氧化物的相互作用。产物分析。
J Biol Chem. 1972 May 25;247(10):3353-60.
6
The crystal structure and molecular stereochemistry of -oxo-bis( , , , -tetraphenylporphinatoiron (3)).
J Am Chem Soc. 1972 May 17;94(10):3620-6. doi: 10.1021/ja00765a060.
7
Oxidation of ferric porphyrins.铁卟啉的氧化作用。
Ann N Y Acad Sci. 1973;206:504-15. doi: 10.1111/j.1749-6632.1973.tb43233.x.
8
A study of solvent and substituent effects on the redox potentials and electron-transfer rate constants of substituted iron meso-tetraphenylporphyrins.关于溶剂和取代基对取代的中-四苯基铁卟啉的氧化还原电位和电子转移速率常数影响的研究。
J Am Chem Soc. 1976 Dec 22;98(26):8387-90. doi: 10.1021/ja00442a013.
9
Peroxidase-catalyzed halogenation.过氧化物酶催化卤化反应。
Annu Rev Biochem. 1976;45:861-88. doi: 10.1146/annurev.bi.45.070176.004241.
10
Horseradish peroxidase compound I: evidence for spin coupling between the heme iron and a 'free' radical.辣根过氧化物酶化合物I：血红素铁与“游离”自由基之间自旋耦合的证据。
FEBS Lett. 1979 Jul 1;103(1):102-5. doi: 10.1016/0014-5793(79)81259-4.
Zotero 插件