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高价咕啉金属配合物

High-valent corrole metal complexes.

作者信息

Gross Z

机构信息

Department of Chemistry and Institute of Catalysis Science and Technology, Technion, Haifa, Israel.

出版信息

J Biol Inorg Chem. 2001 Sep;6(7):733-8. doi: 10.1007/s007750100273.


DOI:10.1007/s007750100273
PMID:11681707
Abstract

This commentary concentrates on corrole complexes with the three metal ions that are most relevant to oxidation catalysis: chromium, manganese, and iron. Particular emphasis is devoted to the only recently introduced meso-triarylcorroles and a comparison with the traditionally investigated beta-pyrrole-substituted corroles. Based on a combination of spectroscopic methods, electrochemistry, and X-ray crystallography, it is concluded that in most high-valent metallocorroles the corrole is not oxidized. Both experimental (for (oxo)chromium(V) corrole) and computational (for (oxo)manganese(V) corrole) evidence indicate that the stabilization of high-valent metal ions by corroles originates from a combination of short metal-nitrogen bonds and large metal out-of-plane displacements in the corrole, which lead to quite unexpected interactions of the oxo-metal pi* orbitals with the in-plane orbitals of the corrole.

摘要

本评论聚焦于与氧化催化最相关的三种金属离子形成的卟吩配合物:铬、锰和铁。特别强调了最近才引入的中位三芳基卟吩,并将其与传统研究的β-吡咯取代卟吩进行比较。基于光谱方法、电化学和X射线晶体学的综合研究,得出结论:在大多数高价金属卟吩中,卟吩并未被氧化。实验证据(对于(氧代)铬(V)卟吩)和计算证据(对于(氧代)锰(V)卟吩)均表明,卟吩对高价金属离子的稳定作用源于金属-氮短键和卟吩中金属平面外大位移的共同作用,这导致氧代金属π*轨道与卟吩平面内轨道产生了相当意外的相互作用。

相似文献

[1]
High-valent corrole metal complexes.

J Biol Inorg Chem. 2001-9

[2]
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[3]
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[4]
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[5]
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[6]
Electronic absorption, resonance Raman, and electrochemical studies of planar and saddled copper(III) meso-triarylcorroles. Highly substituent-sensitive Soret bands as a distinctive feature of high-valent transition metal corroles.

J Am Chem Soc. 2002-7-10

[7]
The electronic structure of iron corroles: a combined experimental and quantum chemical study.

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[8]
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[9]
Significant effect of spin flip on the oxygen atom transfer reaction from (oxo)manganese(V) corroles to thioanisole: insights from density functional calculations.

Phys Chem Chem Phys. 2012-10-5

[10]
Visible light-induced formation of corrole-manganese(V)-oxo complexes: Observation of multiple oxidation pathways.

J Inorg Biochem. 2016-10

引用本文的文献

[1]
Iron Corrole-Catalyzed Intramolecular Amination Reactions of Alkyl Azides. Spectroscopic Characterization and Reactivity of [Fe(Cor)(NAd)].

Adv Sci (Weinh). 2024-10

[2]
Regioselective thiocyanation of corroles and the synthesis of gold nanoparticle-corrole assemblies.

Nanoscale Adv. 2019-11-21

[3]
Metallotexaphyrins as MRI-Active Catalytic Antioxidants for Neurodegenerative Disease: A Study on Alzheimer's Disease.

Chem. 2020-3-12

[4]
Biomimetic Reactivity of Oxygen-Derived Manganese and Iron Porphyrinoid Complexes.

Chem Rev. 2017-11-8

[5]
Lewis-Acid-assisted Hydrogen Atom Transfer to Manganese(V)-Oxo Corrole through Valence Tautomerization.

ChemistryOpen. 2016-10-28

[6]
Control of clustering behavior in anionic cerium(iii) corrole complexes: from oligomers to monomers.

Dalton Trans. 2016-11-22

[7]
Challenging Density Functional Theory Calculations with Hemes and Porphyrins.

Int J Mol Sci. 2016-4-7

[8]
Rhenium(V)-oxo corrolazines: isolating redox-active ligand reactivity.

Chem Commun (Camb). 2016-1-4

[9]
Modulation of the molecular spintronic properties of adsorbed copper corroles.

Nat Commun. 2015-6-26

[10]
Reactivity and O2 Formation by Mn(IV)- and Mn(V)-Hydroxo Species Stabilized within a Polyfluoroxometalate Framework.

J Am Chem Soc. 2015-7-15

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