Synthesis of Phosphine Ligands via a Coordination Assembly Strategy and Their Applications in Hydroformylation

doi:10.6023/cjoc202412013

Abstract

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

Cite this article

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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Fig. & Tab. 3

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

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

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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