| 谢叶叶,兰永成,刘建华,黄志威,夏春谷.新型氮杂环卡宾锌配合物催化CO2和环氧化物高效合成环状碳酸酯[J].分子催化,2023,37(6):545-558 |
| 新型氮杂环卡宾锌配合物催化CO2和环氧化物高效合成环状碳酸酯 |
| Efficient Synthesis of Cyclic Carbonates from CO2 and Epoxides Catalyzed by a Novel Nitrogen Heterocyclic Carbene Zinc Complex |
| 投稿时间：2023-09-02 修订日期：2023-09-28 |
| DOI：10.16084/j.issn1001-3555.2023.06.004 |
| 中文关键词: 二氧化碳固定 环状碳酸酯 氮杂卡宾锌配合物 单组份多功能催化剂 |
| 英文关键词:carbon dioxide fixation cyclic carbonate zinc complex of azacarbene single component multifunctional catalyst |
| 基金项目:国家自然科学基金(22272187, 22072166); 中国科学院“西部之光”西部青年学者项目. |
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| 中文摘要: |
| 合成了一系列新型的芘标记含溴亲核阴离子的氮杂环卡宾前驱体化合物, 与卤化锌配位后获得具有CO2捕获能力以及路易斯酸碱位点的NHC-PDBI-ZnX2(X=Cl、Br、I)催化剂, 通过1H NMR、13C NMR、XPS、FT-IR、13C CP-MAS NMR和ICP-AES表征技术对该类催化剂结构和化学性质进行了表征. 氮杂卡宾锌配合物被证明是有效的单组分多功能催化剂, 对环氧丙烷和CO2的环加成反应显示出较高的催化活性和选择性. 最佳活性的NHC-PDBI-ZnI2催化剂在120 ℃、3.0 MPa、2.0 h等较温和条件下, 取得98%以上碳酸丙烯酯收率. 该催化剂还具有优异的底物普适性和循环使用稳定性, 归因于路易斯酸性Zn 2+与NHC-PBDI主链形成的强共价键. 此外, 结合FTIR等表征推测了反应机理, 其中NHC-PDBI-ZnX2的卡宾位吸附活化CO2以及路易斯酸碱位点开环的协同效应促进了环加成反应在无溶剂和助催化剂条件下的有效进行. |
| 英文摘要: |
| A series of novel pyrene labeled nitrogen heterocyclic carbene precursor compounds containing bromine nucleophilic anions were synthesized and coordinated with zinc halide to obtain NHC-PDBI-ZnX2 (X=Cl, Br, I) catalysts with CO2 capture ability and Lewis acid-base sites. The structure and chemical properties of these catalysts were characterized by 1H NMR, 13C NMR, XPS, FT-IR, 13C CP-MAS NMR, and ICP-AES characterization techniques. The azacarbene zinc complex has been proven to be an effective single component multifunctional catalyst, exhibiting high catalytic activity and selectivity for the cycloaddition reaction of epoxy propane and CO2. The NHC-PDBI-ZnI2 catalyst with the best activity achieved a yield of over 98% of propylene carbonate under mild conditions of 120 ℃, 3.0 MPa and 2.0 h. The catalyst also exhibits excellent substrate universality and cyclic stability, attributed to the strong covalent bond formed between Lewis acidic Zn2+and NHC-PBDI main chain. In addition, the reaction mechanism was speculated based on FTIR and other characterizations. Among them, the synergistic effect of NHC-PDBI-ZnX2's carbene adsorption activation of CO2 and Lewis acid-base site ring opening promoted the effective cycloaddition reaction under solvent-free and cocatalyst free conditions. |
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