Heterogeneous catalytic reactions based on single metal–organic framework (MOF) material for the oxidative carboxylation of olefins following a tandem process, which involves the epoxidation of olefins and subsequent epoxide–CO2 cycloaddition, are highly desirable and economical for CO2 chemical fixation. In this work, a new trans-A2B2-type porphyrin ligand, 5,15-di(m-benzoato)-porphyrin (H2DMBP), was successfully synthesized and utilized for constructing a novel, highly porous, and stable Nd-porphyrin MOF, named CSUST-2. (CSUST stands for Changsha University of Science and Technology.) Furthermore, the coordinatively unsaturated Co(II) ions were implanted into the MOF by exploiting the innate non-metallated porphyrin ligands to generate Co(II)@CSUST-2 framework, which was evidenced to act as an efficient recyclable catalyst for oxidative carboxylation of olefins in the presence of tert-butyl hydroperoxide (TBHP) as an oxidant and tetrabutylammonium bromide (n-Bu4NBr) as a co-catalyst under mild conditions (1 atm CO2, 75 °C, and without solvent).

中文翻译：

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用于烯烃催化氧化羧化的新型卟啉配体金属有机骨架的后金属化

基于单一金属-有机骨架 (MOF) 材料的多相催化反应在串联过程中用于烯烃的氧化羧化，包括烯烃的环氧化和随后的环氧化物-CO2 环加成，对于 CO2 化学固定是非常理想和经济的。在这项工作中，成功合成了一种新的反式 A2B2 型卟啉配体 5,15-二(间苯并托)-卟啉 (H2DMBP)，并将其用于构建新型、高多孔、稳定的 Nd-卟啉 MOF，命名为 CSUST-2。（CSUST代表长沙科技大学。）此外，通过利用先天的非金属化卟啉配体生成Co（II）@CSUST-2框架，将配位不饱和Co（II）离子注入MOF中，