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. 2023 Oct 19;15(20):4143.
doi: 10.3390/polym15204143.

Palladium Catalysts Supported in Microporous Phosphine Polymer Networks

Noelia Esteban  1 , Miguel Claros  1 , Cristina Álvarez  1   2   3 , Ángel E Lozano  1   2   3 , Camino Bartolomé  1 , Jesús M Martínez-Ilarduya  1 , Jesús A Miguel  1
Affiliations

Palladium Catalysts Supported in Microporous Phosphine Polymer Networks

Noelia Esteban et al. Polymers (Basel). .

Abstract

A new set of microporous organic polymers (POPs) containing diphosphine derivatives synthesized by knitting via Friedel-Crafts has been attained. These amorphous three-dimensional materials have been prepared by utilizing diphosphines, 1,3,5-triphenylbenzene, and biphenyl as nucleophile aromatic groups, dimethoxymethane as the electrophilic linker, and FeCl3 as a promoting catalyst. These polymer networks display moderate thermal stability and high microporosity, boasting BET surface areas above 760 m2/g. They are capable of coordinating with palladium acetate, using the phosphine derivative as an anchoring center, and have proven to be highly efficient catalysts in Suzuki-Miyaura coupling reactions involving bromo- and chloroarenes under environmentally friendly (using water and ethanol as solvents) and aerobic conditions. These supported catalysts have achieved excellent turnover numbers (TON) and turnover frequencies (TOF), while maintaining good recyclability without significant loss of activity or Pd leaching after five consecutive reaction cycles.

Keywords: Suzuki–Miyaura; knitting; palladium catalyst; phosphine-based POPs.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
General scheme of phosphine POPs synthetized by knitting.
Figure 2
Figure 2
Comparative 1H NMR (CDCl3). Free TPP (top), TPP treated with TFA-d (TPP-H) (middle), and TPP treated with AlCl3 (TPP-Al) (bottom).
Figure 3
Figure 3
Comparative 31P{1H}NMR (CDCl3). Free TPP (top), TPP treated with TFA−d (TPP−H) (middle), and TPP treated with AlCl3 (TPP−Al) (bottom).
Figure 4
Figure 4
ATR−FTIR spectra of phosphine POPs.
Figure 5
Figure 5
WAXS patterns of PP-3.
Figure 6
Figure 6
Nitrogen adsorption (solid symbol) and desorption (open symbol) isotherms of PP supports.
Figure 7
Figure 7
XPS analysis of Pd3d binding energies for Pd@PP3 before (top) and after 2 catalytic cycles of two hours (Pd@PP-3AU) (bottom).
Figure 8
Figure 8
Comparative study between Pd-PP under milder reaction conditions: 15 min., 40 °C and 0.1 mol% of Pd-PP.
Figure 9
Figure 9
Recyclability of Pd@PP-3.
See this image and copyright information in PMC

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