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一种具有锰桨轮节点的钌卟啉金属有机框架用于C(sp)-H键的选择性氧化。

A Ru-porphyrin metal-organic framework with Mn paddlewheel nodes for the selective oxidation of C(sp)-H bonds.

作者信息

Xiao Xiang, Shen Kesheng, Jing Xu, Duan Chunying

机构信息

State Key Laboratory of Fine Chemicals, College of Chemistry, Dalian University of Technology, 116024, P. R. China.

出版信息

Dalton Trans. 2024 Jul 30;53(30):12604-12609. doi: 10.1039/d4dt01332h.

Abstract

The activation and selective functionalization of inert C(sp)-H bonds is fundamental for industrial applications and occupies a very important place in industry, but it remains a great challenge in current synthetic chemistry. In this paper, we report an approach for activating reactive -butyl peroxyl radicals by modifying Ru-porphyrin into metal-organic frameworks (MOFs) for the activation of inert C(sp)-H bonds. Under mild conditions, the Ru-porphyrinyl MOF can activate the peroxyl radical, extracting a hydrogen atom from the inert C(sp)-H bond. Mn paddlewheels with unsaturated coordination sites were introduced into the MOF, and direct oxidative conversion using environmentally friendly oxygen provides a new pathway to activate the inert C(sp)-H bond.

摘要

惰性C(sp) - H键的活化和选择性官能团化对于工业应用至关重要,在工业中占据着非常重要的地位,但在当前的合成化学中仍然是一个巨大的挑战。在本文中,我们报道了一种通过将钌卟啉修饰成金属有机框架(MOF)来活化反应性叔丁基过氧自由基以实现惰性C(sp) - H键活化的方法。在温和条件下,钌卟啉基MOF能够活化过氧自由基,从惰性C(sp) - H键中提取一个氢原子。将具有不饱和配位位点的锰桨轮引入到MOF中,利用环境友好的氧气进行直接氧化转化为活化惰性C(sp) - H键提供了一条新途径。

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