Reinvestigation of the mechanism of dioxygen activation at a MnII(cyclam) center

IF 3.8 2区化学 Q2 BIOCHEMISTRY & MOLECULAR BIOLOGY

Journal of Inorganic Biochemistry Pub Date : 2024-12-09 DOI:10.1016/j.jinorgbio.2024.112809

Tarali Devi , Stefan Mebs , Dibya Jyoti Barman , Amanda Opis-Basilio , Michael Haumann , Kallol Ray

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Abstract

This study deals with the unprecedented reactivity of a [(cyclam)Mn^II(OTf)₂] (3-cis; OTf = CF₃SO_3⁻) with O₂, which, depending on the presence or absence of a hydrogen atom donor like 1-hydroxy-2,2,6,6-tetramethyl-piperidine (TEMPO-H), selectively generates di-μ-oxo Mn(III)Mn(IV) (1) or Mn^IV₂ (2) complexes, respectively. Both dimers have been characterized by different techniques including single-crystal X-ray diffraction, X-ray absorption spectroscopy, and electron paramagnetic resonance. Oxygenation reactions carried out with labeled ¹⁸O₂ and Resonance Raman spectroscopy unambiguously show that the oxygen atoms present in the Mn^IVMn^III dimer originate from O₂. Experimental evidences are provided for a novel method of dioxygen activation involving three Mn ions or two Mn ions and TEMPO-H to generate the bis(μ-oxo)dimanganese(IV) or bis(μ-oxo) dimanganese(III, IV) cores, respectively.

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MnII（cyclam）中心双氧活化机制的再研究。

本文研究了a [(cyclam)MnII(OTf)2] (3-cis；OTf = CF3SO3-)与O2反应，根据是否存在像1-羟基-2,2,6,6-四甲基哌啶（TEMPO-H）这样的氢原子供体，分别选择性地生成di-μ-oxo Mn(III)Mn(IV)(1)或MnIV2(2)配合物。这两种二聚体都用不同的技术进行了表征，包括单晶x射线衍射、x射线吸收光谱和电子顺磁共振。用标记的18O2和共振拉曼光谱进行的氧化反应明确地表明，MnIVMnIII二聚体中的氧原子来自O2。实验证明，采用3个Mn离子或2个Mn离子和TEMPO-H分别生成双（μ-oxo）二锰（IV）或双（μ-oxo）二锰（III， IV）核的双氧活化新方法是可行的。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Journal of Inorganic Biochemistry 生物-生化与分子生物学

CiteScore

7.00

自引率

10.30%

发文量

336

审稿时长

41 days

期刊介绍： The Journal of Inorganic Biochemistry is an established international forum for research in all aspects of Biological Inorganic Chemistry. Original papers of a high scientific level are published in the form of Articles (full length papers), Short Communications, Focused Reviews and Bioinorganic Methods. Topics include: the chemistry, structure and function of metalloenzymes; the interaction of inorganic ions and molecules with proteins and nucleic acids; the synthesis and properties of coordination complexes of biological interest including both structural and functional model systems; the function of metal- containing systems in the regulation of gene expression; the role of metals in medicine; the application of spectroscopic methods to determine the structure of metallobiomolecules; the preparation and characterization of metal-based biomaterials; and related systems. The emphasis of the Journal is on the structure and mechanism of action of metallobiomolecules.