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Updated: Aug 22, 2025
Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
Published on: July 27, 2022
Highly Active Rh Catalysts with Strong π-Acceptor Phosphine-Containing Porous Organic Polymers for Alkene
Miaojiang Wu1,2, Guang Gao1, Chao Yang1
1State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, 730000, China.
Abstract:
Phosphine-containing porous organic polymers (phosphine-POPs) are a kind of potential catalyst support for alkene hydroformylation. However, the synthesis of phosphine-POPs with strong π-acceptor is still a challenge. Herein, we report the synthesis of phosphine-POPs with different π-acceptor properties [POL-P(Pyr)3, CPOL-BPa&PPh3-15, and CPOL-BP&PPh3-15] and evaluated their performances as ligands to coordinate with Rh(acac)(CO)2 for hydroformylation of alkenes. We found that the Rh center with stronger π-acceptor phosphine-POPs showed better catalytic performance. Rh/CPOL-BPa&PPh3-15 with strong π-acceptor bidentate phosphoramidites showed obviously higher activity and regioselectivity (TON = 7.5 × 103, l/b = 26.1) than Rh/CPOL-BP&PPh3-15 (TON = 5.3 × 103, l/b = 5.0) with weaker π-acceptor bidentate phosphonites. Particularly, the TON of the hydroformylation reached 27.7 × 103 upon using Rh/POL-P(Pyr)3 which possessed tris(1-pyrrolyl)phosphane coordination sites. Overall, our study provides an orientation to design phosphine-POPs for hydroformylation reactions.
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