Bis(pyrazolyl)methane supported Cu(II) catalysts for biomimetic catalytic oxidation reactions

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta Pub Date : 2025-05-15 DOI:10.1016/j.ica.2025.122753

S. Nakul , R. Bhagavatish , R. Anjali , Sam John , Jomon Mathew , Naveen V. Kulkarni

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引用次数: 0

Abstract

Two copper (II) complexes, [Cu(L1)(Cl)₂(H₂O)₂] (C1) and [Cu(L2)₂(Cl)(H₂O)]Cl (C2) synthesized by reacting bis(3,5-dimethyl-1H-pyrazol-1-yl)methane (L1) and bis(1H-pyrazol-1-yl)methane (L2) ligands with copper chloride dihydrate in methanol at room temperature, were employed as catalysts in the biomimetic oxidation reactions and their catalytic efficiency was investigated. The complex C1 was found to be highly efficient in mimicking the catalytic action of the enzyme catechol oxidase (CO) in the oxidation of 3,5-di-tert butyl catechol (3,5-DTBC) and the enzyme phenoxazinone synthase (PHS) in the oxidative coupling of 2-amino phenol (2-AP). The influence of solvent and pH on the catalytic reactions was also investigated. Comprehensive kinetic studies were carried out to understand the mechanism of catalytic reactions. Iodine-test and ESR experiments as well as DFT-energy profiling were carried out to support the proposed reaction mechanism.

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双（吡唑基）甲烷负载Cu（II）催化剂用于仿生催化氧化反应

以双（3,5-二甲基- 1h -吡唑-1-基）甲烷（L1）和双（1h -吡唑-1-基）甲烷（L2）为配体，在甲醇中与二水氯化铜室温反应合成了[Cu(L1)(Cl)2(H2O)2] （C1）和[Cu(L2)2(Cl)(H2O)]Cl （C2）两种铜（II）配合物，作为仿生氧化反应的催化剂，考察了它们的催化效率。配合物C1能高效模拟邻苯二酚氧化酶（CO）氧化3,5-二叔丁基邻苯二酚（3,5- dtbc）和苯氧杂嗪酮合成酶（PHS）氧化偶联2-氨基酚（2-AP）的催化作用。考察了溶剂和pH对催化反应的影响。进行了全面的动力学研究，以了解催化反应的机理。碘测试和ESR实验以及dft能量谱分析支持了所提出的反应机理。

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来源期刊

Inorganica Chimica Acta 化学-无机化学与核化学

CiteScore

6.00

自引率

3.60%

发文量

440

审稿时长

35 days

期刊介绍： Inorganica Chimica Acta is an established international forum for all aspects of advanced Inorganic Chemistry. Original papers of high scientific level and interest are published in the form of Articles and Reviews. Topics covered include: • chemistry of the main group elements and the d- and f-block metals, including the synthesis, characterization and reactivity of coordination, organometallic, biomimetic, supramolecular coordination compounds, including associated computational studies; • synthesis, physico-chemical properties, applications of molecule-based nano-scaled clusters and nanomaterials designed using the principles of coordination chemistry, as well as coordination polymers (CPs), metal-organic frameworks (MOFs), metal-organic polyhedra (MPOs); • reaction mechanisms and physico-chemical investigations computational studies of metalloenzymes and their models; • applications of inorganic compounds, metallodrugs and molecule-based materials. Papers composed primarily of structural reports will typically not be considered for publication.