基于质子耦合电子转移的仿生氧化催化：甲烷高效选择性氧化制甲醇的研究

IF 3.2 2区化学 Q2 BIOCHEMISTRY & MOLECULAR BIOLOGY

Journal of Inorganic Biochemistry Pub Date : 2025-02-21 DOI:10.1016/j.jinorgbio.2025.112856

Takahiko Kojima

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引用次数: 0

摘要

本文从FeIII-TPA （TPA =三（2-吡啶基甲基）胺）配合物与烷基氢过氧化物氧化烷烃为ru -吡啶胺配合物开始，通过质子耦合电子转移氧化相应的rui -aqua配合物可转化为不同自旋态（S = 1或0）的ruii -氧配合物，阐明了这些自旋态不影响其在水中的反应性。引入强给体n -杂环羰基（NHC）基团，可以得到与ruiv -氧配合物反应性不同的ruiii -氧配合物。还描述了Ru-TPA配合物的第二配位球（scs）的操作，可视化独特的功能。将疏水SCS引入到fei - nhc配合物中，可以基于“捕获-释放”策略，在水介质中催化甲烷选择性氧化生成高选择性甲醇，这也可以使我们实现芳香族化合物的高选择性双电子氧化。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Bio-inspired oxidation catalysis based on proton-coupled electron transfer: Toward efficient and selective oxidation of methane to methanol

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Bio-inspired oxidation catalysis based on proton-coupled electron transfer: Toward efficient and selective oxidation of methane to methanol

In this paper, a trail of my research is described starting from oxidation of alkanes by Fe^III-TPA (TPA = tris(2-pyridylmethyl)amine) complexes with alkyl hydroperoxides to Ru-pyridylamine complexes which can be converted to Ru^IV-oxo complexes in different spin states (S = 1 or 0) through proton-coupled electron-transfer oxidation of the corresponding Ru^II-aqua complexes, clarifying that those spin states do not affect the reactivity in water. The introduction of strongly donating N-heterocyclic carbene (NHC) moiety allows us to create a Ru^III-oxyl complex showing different reactivity from that of Ru^IV-oxo complexes. Manipulation of second coordination spheres (SCSs) of Ru-TPA complexes is also described, visualizing unique functionality. The introduction of hydrophobic SCS to a Fe^II-NHC complex enables to catalyze selective oxidation of methane to form methanol in high selectivity in aqueous media based on the “catch-and-release” strategy, which can also allow us to achieve highly selective two-electron oxidation of aromatic compounds.

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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.