Controllable Cyclopalladated Polythiophene Imine Monolayer by Self-Assembly, Hybrid Doping and Electrochemical Polymerization: A Simple Way to Enhance Activity and Stability

Huang, Louguangshu; Liu, Hui; Xue, Xiaoxia; Zhao, Wei; Li, Tiesheng

doi:10.21926/cr.2201003

Cited by 6 publications

(2 citation statements)

References 34 publications

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“…Studies have demonstrated that the catalytic activity of the mono-or bi-organometallic catalytic monolayers can be improved by quantifying film morphology, tuning the composition of different metals, elucidating the relative distributions of electrons (which are related to the electrical characteristics of the ligand), and modifying the support and synergy of hetero-bimetals [18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35]. Appropriate supports, such as silicon with a greater flat surface, can result in a high dispersion and reproducibility of ordered organometallic catalytic monolayers [21-23, 25, 36-38].…”

Section: Introductionmentioning

confidence: 99%

Fabrication and Catalytic Property of an Ordered Terpyridine Pd(II)/Ni(II) Catalytic Monolayer for Suzuki Coupling Reactions

Wang¹,

Bi²,

Li³

et al. 2022

Catal Res

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Fabrication, arrangement, and controllable composition of ordered organometallic films are critical for designing a highly active catalyst and investigating the catalytic mechanism. In this paper, an organometallic terpyridine Pd(II)/Ni(II) monolayer linked on the silicon substrate surface (denoted as Si-Tpy-Pd1/Ni1) was prepared and characterized using water contact angle, ultraviolet spectra, X-ray diffraction, scanning electron microscopy, and X-ray photoelectron microscopy. Si-Tpy-Pd1/Ni1 exhibited high catalytic activity, substrate applicability, and reusability after 5 runs. During recycling, the deactivation was induced by the aggregation of active Pd/Ni nanoparticles. The catalytic mechanism was heterogeneous and occurred on the Si-Tpy-Pd1/Ni1 monolayer surface; the mechanism was confirmed using hot filtrate, poison test, and a three-phase experiment. The real active center was Pdδ–/Niδ+ and was formed in situ on the organometallic monolayer surface, which acted as a precursor with a synergistic effect between Pd and Ni. The electron density of Pd became more negative because of electron transfer from Ni to Pd, which facilitated the oxidative addition reaction.

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Section: Introductionmentioning

confidence: 99%

Fabrication and Catalytic Property of an Ordered Terpyridine Pd(II)/Ni(II) Catalytic Monolayer for Suzuki Coupling Reactions

Wang¹,

Bi²,

Li³

et al. 2022

Catal Res

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“…Cyclopalladated ferrocenylimine and its selfassembly monolayer are the most efficient catalysts in Suzuki coupling reactions [25,26]. Catalytic monolayers with different ligands with Schiff-base groups and their complexes are used to catalyze coupling reactions [13,14,[27][28][29][30][31][32][33][34][35][36][37]. However, a few studies on chiral cyclopalladated brushes immobilized on supports in a coupling reaction in heterogeneous were reported [38][39][40][41].…”

Section: Introductionmentioning

confidence: 99%

A New Chiral Cyclopalladated Ferrocenylimine Self-assembly Polymeric Film supported on Silicon for Heck and Suzuki-coupling Reactions

Wang¹,

Liu²,

Li³

et al. 2022

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A new chiral cyclopalladated ferrocenyl imine catalyst (called 4a2) was designed and synthesized, and its self-assembly catalytic polymeric brush supported on silicon (denoted as Si@PB4a2) was also fabricated by surface-initiated atom transfer radical polymerization (ATRP) and characterized. The catalytic properties of monomer 4a2 in homogeneous and Si@PB4a2 in heterogeneous in Heck and Suzuki cross-coupling were investigated, respectively. They exhibited higher catalytic activity in Heck, and Suzuki coupling reactions in homogeneous and heterogeneous using water as the solvent, and the catalytic activity of Si@PB4a2 with a turn of number (TON,11933 molproduct/molcat) in heterogeneous was 200 times more than that of 4a2 in homogeneous due to the ordered arrangement of the catalyst supported on silicon. Si@PB4a2 had high recyclability, i.e., at least eight runs and six runs, in Suzuki and Heck coupling reactions, respectively.

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Self‐assembly aryl cyclopalladated imine film supported on the silicon surface—Fabrication, formation of active PdPd/PdO sites, and catalytic properties for Sonogashira cross‐coupling reaction

Guo,

He,

Zhang

et al. 2024

Applied Organom Chemis

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Tailoring the structure and arrangement of the organometallic catalyst are essential for the fundamental investigating and applications, and the impacting challenges, such as the size, active species distribution, and composition, as well as the orientation of catalyst, are critical for determining their activities and efficiencies. Herein, a series of aryl cyclopalladated catalysts containing different alkane chains were synthesized, and their self‐assembly films covalent binding to the silicon surface were fabricated and characterized with water drop contact angle, Raman, atomic force microscopy, scanning electron microscopy, and X‐ray photoelectron spectroscopy. The catalytic performances of these catalytic films were explored using Sonogashira cross‐coupling reaction as a template. One of these catalytic films exhibited a higher catalytic activity with a TON value of up to 68,333 h−1, which was 20 times higher than that of homogeneous catalyst due to the ordered arrangement of this catalyst on the silicon surface, and could be reused at least seven times. The catalytic mechanism was heterogeneous catalysis occurred at interface confirmed by hot filtration tests, poisoning tests, and ReactIR. The real active site was PdPd/PdO, and the synergistic effect between Pd and PdO in the active sites (PdPd/PdO) made the key initial oxidation step easily proceed, improving its catalytic activity. The loss of active sites and residues absorbed on the surface of catalytic film were the main reason for deactivation.

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Controllable Cyclopalladated Polythiophene Imine Monolayer by Self-Assembly, Hybrid Doping and Electrochemical Polymerization: A Simple Way to Enhance Activity and Stability

Cited by 6 publications

References 34 publications

Fabrication and Catalytic Property of an Ordered Terpyridine Pd(II)/Ni(II) Catalytic Monolayer for Suzuki Coupling Reactions

Fabrication and Catalytic Property of an Ordered Terpyridine Pd(II)/Ni(II) Catalytic Monolayer for Suzuki Coupling Reactions

A New Chiral Cyclopalladated Ferrocenylimine Self-assembly Polymeric Film supported on Silicon for Heck and Suzuki-coupling Reactions

Self‐assembly aryl cyclopalladated imine film supported on the silicon surface—Fabrication, formation of active PdPd/PdO sites, and catalytic properties for Sonogashira cross‐coupling reaction

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