Heterogeneous visible-light photoredox catalysis with NiCl2@g-C3N4 for induced C(sp2)-H/NH cross-dehydrogenative coupling

IF 3.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis Pub Date : 2024-10-25 DOI:10.1016/j.mcat.2024.114633

Lipeng Li , Xiuzhi Xu , Jin Wang, Jianjun Kang, Yan Chen, Fang Ke

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Abstract

A novel photoactive NiCl₂@g-C₃N₄ catalyst system, which effectively drives C(sp²)-H/NH bond formation between quinolin-2(1H)-ones, primary and secondary aliphatic amines under blue light irradiation. The NiCl₂@g-C₃N₄ composite with a NiCl₂ loading of 0.7wt% had the highest photoactivity, and the calculated band gap energy value is 2.56 eV The nickel ion could act as an electron acceptor enhancing carrier separation and transfer efficiency, greatly enhanced the photoreaction efficiency of g-C₃N₄. Preliminary mechanistic studies indicate upon visible light irradiation, the photo-generated electrons and holes act as oxidants, thereby generating amine radicals in the absence of external chemical oxidants. This provides a straightforward and efficient approach for directly 3-aminating quinoxalines-2(1H)-ones. Moreover, the heterogeneous catalyst can be recycled at least six times without significant activity loss.

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利用NiCl2@g-C3N4进行异相可见光光氧化催化，诱导C（sp2）-H/NH交叉脱氢偶联

一种新型光活性 NiCl2@g-C3N4 催化剂体系，可在蓝光照射下有效驱动喹啉-2(1H)-酮、伯胺和仲胺之间形成 C(sp2)-H/NH 键。镍含量为 0.7wt% 的 NiCl2@g-C3N4 复合材料具有最高的光活性，其计算带隙能值为 2.56 eV。初步的机理研究表明，在可见光照射下，光产生的电子和空穴可作为氧化剂，从而在没有外部化学氧化剂的情况下产生胺自由基。这为直接 3-氨基化喹喔啉-2(1H)-酮提供了一种直接而有效的方法。此外，这种异相催化剂可以循环使用至少六次，而不会有明显的活性损失。

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来源期刊

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