Alkane hydroxylation by m-CPBA catalyzed by Co(II)-complexes

IF 4.9 2区 化学 Q2 CHEMISTRY, PHYSICAL Molecular Catalysis Pub Date : 2025-02-01 Epub Date: 2024-12-24 DOI:10.1016/j.mcat.2024.114782
Takumi Nakamura, Rin Ito, Hideki Sugimoto, Shinobu Itoh
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Abstract

Catalytic activities of the cobalt(II) complexes supported by tripodal N4-tetradentate ligands have been examined in the alkane hydroxylation reaction by m-CPBA (m-chloroperbenzoic acid). Detailed product analysis data have indicated that hydrogen atom abstraction (HAA) from the alkane substrates is a key step in the hydroxylation reaction, where not only the aroyloxy radical intermediate (ArC(O)O•; Ar = m-chlorophenyl)) derived from m-CPBA via O–O bond homolysis but also a Co–O• type intermediate is involved as a reactive oxidant. Significant effects of the supporting ligands and the metal ions (FeII, NiII, and CuII) support this mechanism.

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Co(II)配合物催化m-CPBA的烷烃羟基化反应
研究了三足n4 -四齿配体负载的钴(II)配合物在m-CPBA(间氯过苯甲酸)烷烃羟基化反应中的催化活性。详细的产物分析数据表明,从烷烃底物中提取氢原子(HAA)是羟基化反应的关键步骤,其中不仅有芳氧基自由基中间体(ArC(O)O•;Ar = m-氯苯基))通过O-O键均裂由m-CPBA衍生,但也有Co-O•型中间体作为活性氧化剂参与。支持配体和金属离子(FeII, NiII和CuII)的显著作用支持了这一机制。
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来源期刊
Molecular Catalysis
Molecular Catalysis Chemical Engineering-Process Chemistry and Technology
CiteScore
6.90
自引率
10.90%
发文量
700
审稿时长
40 days
期刊介绍: Molecular Catalysis publishes full papers that are original, rigorous, and scholarly contributions examining the molecular and atomic aspects of catalytic activation and reaction mechanisms. The fields covered are: Heterogeneous catalysis including immobilized molecular catalysts Homogeneous catalysis including organocatalysis, organometallic catalysis and biocatalysis Photo- and electrochemistry Theoretical aspects of catalysis analyzed by computational methods
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