Controlled Cationic Polymerization with Organotellurium Catalysts Utilizing Redox-Mediated Chalcogen Bonding Interaction DOI
Koji Takagi, Shuhei Hayashi,

Nao Sakakibara

et al.

Macromolecules, Journal Year: 2024, Volume and Issue: 57(7), P. 3358 - 3367

Published: March 22, 2024

The electrochemical oxidation behavior of organotellurium compounds (DAnT, POxT, PThT, and PAzT) the structure–property relationships resulting cationic species were evaluated by cyclic voltammetry electro spin resonance measurements density functional theory calculations. [POxT2]2+ obtained from POxT was found to have a highly active chalcogen bonding (ChB) potency as evidenced large Vs,max value (186.4 kcal·mol–1). While neutral has no catalytic activity, electrochemically generated applying an potential at 0.68 V vs Ag/Ag+ can activate carbon–chlorine bond propagating chain ends p-methylstyrene (pMeS) through ChB interaction, in complete monomer conversion 0 °C 1 h give poly(pMeS) with theoretical molecular weight (Mn = 6100) relatively narrow distribution (Mw/Mn 1.49). PAzT could not bring about polymerization pMeS, but p-methoxystyrene (pMOS) higher ability smoothly consumed afford poly(pMOS) having Mn 9400 Mw/Mn 1.94. counteranion supporting electrolyte influenced behavior; namely, application Bu4NPF6 induced controlled pMeS polymer be determined feed ratio. Importantly, control over growth achieved reversibly switching direction current flow cell between (ON state) −0.30 (OFF state).

Language: Английский

Halogen, Chalcogen, Pnictogen, and Tetrel Bonding in Non‐Covalent Organocatalysis: An Update DOI Creative Commons
Dragana Jovanovic,

Meghana Poliyodath Mohanan,

Stefan M. Huber

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(31)

Published: May 11, 2024

The use of noncovalent interactions based on electrophilic halogen, chalcogen, pnictogen, or tetrel centers in organocatalysis has gained noticeable attention. Herein, we provide an overview the most important developments last years with a clear focus experimental studies and catalysts which act via such non-transient interactions.

Language: Английский

Citations

29
A Fluorogenic Substrate for Quinoline Reduction: Pnictogen‐Bonding Catalysis in Aqueous Systems DOI Creative Commons
Giacomo Renno, Qingxia Zhang, Antonio Frontera

et al.

Helvetica Chimica Acta, Journal Year: 2024, Volume and Issue: 107(5)

Published: March 6, 2024

Abstract It is often said that pnictogen‐bonding catalysis, and σ ‐hole catalysis in general, would not work aqueous systems because the solvent interfere as an overcompetitive pnictogen‐bond acceptor. In this study, we show transfer of from hydrophobic solvents to possible by replacing only with hydrophilic substrates, without changing catalyst or reaction. This differs conventional covalent Lewis acid catalysts, which are instantaneously destroyed ligand exchange. With their water‐proof substituents place exchangeable ligands, supramolecular counterpart evinced catalyze hydrogenation quinolines neutral systems. To secure these results, introduce a water‐soluble fluorogenic substrate releases coumarin upon reduction instead activated quinolidiniums, stiborane catalysts deepened holes. They demonstrate can operate higher‐order architectures for under biologically relevant conditions, provide operational assay high‐throughput screening fluorescence imaging, situ conditions.

Language: Английский

Citations

5
Nichtkovalente Organokatalyse mit Halogen‐, Chalkogen‐, Pniktogen‐ und Tetrelbrücken: neuere Entwicklungen DOI Creative Commons
Dragana Jovanovic,

Meghana Poliyodath Mohanan,

Stefan M. Huber

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(31)

Published: May 10, 2024

Abstract Die Anwendung nichtkovalenter Wechselwirkungen, welche auf elektrophilen Halogen‐, Chalkogen‐, Pniktogen‐ oder Tetrelzentren beruhen, hat in der Organokatalyse deutlich an Aufmerksamkeit gewonnen. Wir geben hier einen Überblick über die wichtigsten Entwicklungen letzten Jahre, mit einem Fokus experimentellen Studien und Katalysatoren, nicht‐transiente derartige Welchselwirkungen agieren.

Citations

2
Controlled Cationic Polymerization with Organotellurium Catalysts Utilizing Redox-Mediated Chalcogen Bonding Interaction DOI
Koji Takagi, Shuhei Hayashi,

Nao Sakakibara

et al.

Macromolecules, Journal Year: 2024, Volume and Issue: 57(7), P. 3358 - 3367

Published: March 22, 2024

The electrochemical oxidation behavior of organotellurium compounds (DAnT, POxT, PThT, and PAzT) the structure–property relationships resulting cationic species were evaluated by cyclic voltammetry electro spin resonance measurements density functional theory calculations. [POxT2]2+ obtained from POxT was found to have a highly active chalcogen bonding (ChB) potency as evidenced large Vs,max value (186.4 kcal·mol–1). While neutral has no catalytic activity, electrochemically generated applying an potential at 0.68 V vs Ag/Ag+ can activate carbon–chlorine bond propagating chain ends p-methylstyrene (pMeS) through ChB interaction, in complete monomer conversion 0 °C 1 h give poly(pMeS) with theoretical molecular weight (Mn = 6100) relatively narrow distribution (Mw/Mn 1.49). PAzT could not bring about polymerization pMeS, but p-methoxystyrene (pMOS) higher ability smoothly consumed afford poly(pMOS) having Mn 9400 Mw/Mn 1.94. counteranion supporting electrolyte influenced behavior; namely, application Bu4NPF6 induced controlled pMeS polymer be determined feed ratio. Importantly, control over growth achieved reversibly switching direction current flow cell between (ON state) −0.30 (OFF state).

Language: Английский

Citations

1