配位组装策略合成膦配体及其在氢甲酰化中的应用

doi:10.6023/cjoc202412013

摘要/Abstract

传统的膦配体由共价键形成, 基于超分子组装策略构建新型膦配体的方法具有更加方便和快捷的优点, 受到广泛关注. 本工作采用配位组装的策略, 设计合成了5种由钳形氮与Fe(Ⅱ)配位组装而成的新型膦配体, 使用NMR、FT-IR、UV-Vis等对其结构进行了表征, 并结合计算化学方法对其稳定构型进行了模拟推测. 结果表明, 通过对组装模块结构的调变, 可实现对该组装膦配体构型的调控, 为自组装模块化构建多样性膦配体提供了一种有效的方法. 该组装配体修饰的铑催化剂在烯烃氢甲酰化反应中表现出良好的催化活性和选择性. 根据催化数据和表征结果, 对该组装膦配体中的磷原子与铑的可能配位模式进行了探讨.

关键词: 配位, 组装, 膦配体, 氢甲酰化

Traditional phosphine ligands are constituted by covalent bonds. Constructions of novel phosphine ligands through supramolecular assembly strategies have attracted a widespread attention. This study utilized a coordination assembly strategy to design and synthesize five kinds of phosphine ligands, which were assembled from different phosphorus-containing pincer nitrogen ligands and Fe(Ⅱ). Their structures were characterized by NMR, FT-IR, and UV-Vis measurements, and their thermodynamic stablized configurations were determined through density functional theory (DFT) calculation. The results demonstrated that modulating the structure of the assembly modules enables control over the configurations of the assembled phosphine ligands, providing an effective method for modular construction of diverse phosphine ligands. The rhodium catalysts modified with these assembled ligands exhibited excellent catalytic activity and selectivity in hydroformylation of olefins. Based on catalytic data and characterization results, the possible coordination modes between phosphorus atoms in the assembled phosphine ligands and rhodium were discussed.

Key words: coordination, assembly, phosphine ligand, hydroformylation

引用此文

刘祖恋, 杨德玺, 房虎, 薛卫超, 付海燕, 李瑞祥, 郑学丽, 陈华. 配位组装策略合成膦配体及其在氢甲酰化中的应用[J]. 有机化学, 2025, 45(8): 2960-2967.

Zulian Liu, Dexi Yang, Hu Fang, Weichao Xue, Haiyan Fu, Ruixiang Li, Xueli Zheng, Hua Chen. Synthesis of Phosphine Ligands via a Coordination Assembly Strategy and Their Applications in Hydroformylation[J]. Chinese Journal of Organic Chemistry, 2025, 45(8): 2960-2967.

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图/表 3

图1. (a) L1~L3的合成路线; (b) L1的扩散排序谱图; (c) L1的高分辨质谱图; (d) L2的扩散排序谱图; (e) L2的高分辨质谱图; (f) L3的扩散排序谱图; (g) L3的高分辨质谱图

Figure 1. (a) Synthetic routes of L1~L3; (b) Diffusion-ordered spectroscopy (DOSY) of L1; (c) High-resolution ESI-MS spectrum of L1; (d) Diffusion-ordered spectroscopy of L2; (e) High-resolution ESI-MS spectrum of L2; (f) Diffusion-ordered spectroscopy of L3; (g) High-resolution ESI-MS spectrum of L3

图2. DFT优化所得的L1~L3能量最低构型

Figure 2. Energy-minimized configurations of L1~L3 obtained from DFT optimization

图3. (a) 1-己烯的氢甲酰化反应; (b) L1参与的不同烯烃的氢甲酰化反应

Figure 3. (a) Hydroformylation reaction of 1-hexene; (b) Hydroformylation reactions of different olefins involving L1 Reaction conditions: (a) 1-hexene (4.0 mmol), Rh(acac)(CO)2 (4×10－3 mmol), H2/CO (V∶V=1∶1), toluene (3.0 mL), 5 h. (Ⅰ) 90 ℃, 1 MPa; (Ⅱ) n(P)∶n(Rh)=4∶1, 1 MPa; (Ⅲ) n(P)∶n(Rh)=4∶1, 90 ℃; (Ⅳ) n(P)∶n(Rh)=4∶1, 90 ℃, 1 MPa; (b) Substrate (4.0 mmol), n(P)∶n(Rh)=4∶1, Rh(acac)(CO)2 (4×10－3 mmol), H2/CO (V∶V=1∶1), 90 ℃, 2 MPa, toluene (3.0 mL), 12 h.

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