Solvent-modulated Binding Selectivity of Reaction Substrates to Onium-based Sigma-Hole Donors DOI Creative Commons
Alexandra A. Sysoeva, Alexander S. Novikov, Dmitrii S. Bolotin

et al.

Published: Dec. 20, 2022

Combination of experimental data and results DFT calculations indicates that the catalytic activity chalconium halonium salts served as sigma-hole donating organocatalysts cannot be clearly estimated via analysis electrostatic potential on catalysts’ sigma-holes values catalyst•••TS intermolecular interactions, such polarization effects, charge transfer, or covalency bonding. Moreover, real effect might not correlate well with Gibbs free energies activation reactions, because solvation effects other competitive binding processes play at least same even more important role in catalysis. It was showed present work, either can lead to increase equilibrium concentration reactive catalyst•••electrophile associates thus accelerating reaction brings favorable generation catalyst•••nucleophile species resulting suppression organocatalyst.

Language: Английский

Computational Study on the Route of Cooperative Organocatalysis Utilizing Thiourea and Halogen Bond Donor Mixture DOI
Alexander S. Novikov, Mikhail V. Il’in

Russian Journal of General Chemistry, Journal Year: 2024, Volume and Issue: 94(S1), P. S129 - S137

Published: Jan. 1, 2024

Language: Английский

Citations

2
Mechanistic Insight into Anion‐Binding Catalytic Living Cationic Polymerization DOI Open Access
Maosheng Li, Hongyu Li, Xiaoyong Zhang

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(26)

Published: April 26, 2023

Abstract Exploiting non‐covalent interactions to catalyze challenging ionic polymerizations is an ambitious goal but in its infancy. We recently demonstrated anion‐binding catalysis as effective methodology enable living cationic polymerization (LCP) of vinyl ethers environmentally benign manner. Here, we further elucidate the structure‐reactivity relationships elaborately designed seleno‐cyclodiphosph(V)azanes catalysts and roles by a combined theoretical DFT study experimental study. The investigation suggests that distinct cis ‐cyclodiphosph(V)azane framework with “selenium effect” electron‐withdrawing 3,5‐(CF 3 ) 2 ‐Phenyl substitution pattern catalyst enables critical contribution accessing excellent stability, anion affinity solubility under conditions. Thus, could leverage precisely control reversible transient dormant‐active species equilibrium, allowing it dynamically bind, recognize pre‐organize propagating monomer, thereby facilitating efficient chain propagation minimizing irreversible transfer events mild more in‐depth understanding mechanism for catalytic LCP reported herein should help guide future design extend this concept broader systems where serve crucial intermediates.

Language: Английский

Citations

4
Pnictogen bonding‐mediated controlled cationic polymerization of styrene derivatives: Catalytic activity investigation using non‐ionic and ionic pnictogen compounds DOI Open Access

Tomoki Hasegawa,

Koji Takagi

Journal of Polymer Science, Journal Year: 2023, Volume and Issue: 61(21), P. 2655 - 2664

Published: Aug. 14, 2023

Abstract The cationic polymerization of p ‐methoxystyrene (pMOS) was carried out at 25°C using pMOS·HCl and Sb(C 6 F 5 ) 3 . Under the condition [pMOS·HCl]:[Sb(C ]:[pMOS] = 10:10:500 in mM concentration, CH CN/CH 2 Cl (3/1 volume ratio) homogeneously proceeded giving rise to poly(pMOS) with M n 5800 w / 1.50. Based on monomer consumption rate, catalytic activity increased order (5.9 × 10 −1 h > Te(C (2.0 IC (1.0 −2 ). In presence Bu 4 NCl (0.02 equivalent relative ), molecular weight distribution became narrower ( 1.23), but MALDI‐TOF/MS implied chain transfer reactions. On other hand, pMOS [MeSbPh ][TEPB] combined resulted better controllability (calculated 6100 theoretical 6300), where reactions were decreased as confirmed by analysis. [SbPh ][OTf] exhibited a activity. [EtOCOCH SbPh electron‐withdrawing ester group showed highest (monomer conversion reached 91% 8 h) while maintaining narrow 1.27). ‐Methylstyrene styrene also polymerized catalyst ][TEPB], although not controlled.

Language: Английский

Citations

4
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
Halogen-Bond-Based Organocatalysis Unveiled: Computational Design and Mechanistic Insights DOI Creative Commons
Nika Melnyk, Marianne Rica Garcia, Cristina Trujillo

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(23), P. 15505 - 15515

Published: Nov. 16, 2023

Halogen-bond-based organocatalysis is a promising alternative to extensively explored hydrogen-bond-based catalysis. This paper presents comprehensive theoretical investigation of the structural and electronic properties σ-hole, as well computational design series electronically activated monodentate bidentate iodine benzimidazolium achiral donor systems, inspired by experimental papers published in past decade. The aforementioned activation modes are compared, mechanistic details reaction discussed.

Language: Английский

Citations

3
Computational Study on the Route of Cooperative Organocatalysis Utilizing Thiourea and Halogen Bond Donor Mixture DOI Creative Commons
Alexander S. Novikov, Dmitrii S. Bolotin

Published: Aug. 1, 2023

A computational analysis of possible routes cooperative catalysis involving hydrogen bond donating thiourea and halogen organocatalysts has been carried out at the M06-2X/SDD level theory using solvation model based on density (SMD). For systems 2-iodoimidazolium or iodonium salt derivatives, previously suggested route including sequential electrophilic activation a reaction electrophile via XB-activated HB donor was ruled out.

Language: Английский

Citations

1
Dual control of stereoregularity and molecular weight in cationic polymerization of vinyl ether by tunable TADDOLs/TiCl4 initiating systems DOI Creative Commons
Hironobu Watanabe,

Y. Mishima,

Arihiro Kanazawa

et al.

Polymer Chemistry, Journal Year: 2024, Volume and Issue: 15(11), P. 1062 - 1069

Published: Jan. 1, 2024

The stereoregularity and molecular weight of poly(isobutyl vinyl ether) was simultaneously controlled by TADDOL/TiCl 4 initiating systems with various aryl substituents on TADDOL.

Language: Английский

Citations

0
Solvent-modulated Binding Selectivity of Reaction Substrates to Onium-based Sigma-Hole Donors DOI Creative Commons
Alexandra A. Sysoeva, Alexander S. Novikov, Mikhail V. Il’in

et al.

Published: Jan. 2, 2023

The combination of experimental data and results DFT calculations indicates that the catalytic activity chalconium halonium salts serving as sigma-hole donating organocatalysts cannot be clearly estimated via analysis electrostatic potential on catalysts’ sigma-holes values catalyst•••TS intermolecular interactions, such polarization effects, charge transfer, or covalency bonding. Moreover, real effect might not correlate well with Gibbs free energy activation reactions, because solvation effects other competitive binding processes play at least an equal even more important role in catalysis. It was shown present work can either lead to increase equilibrium concentration reactive catalyst•••electrophile associates, thus accelerating reaction, brings favorable generation catalyst•••nucleophile species resulting suppression organocatalyst.

Language: Английский

Citations

0
Cooperative Catalysis Involving Hydrogen and Halogen Bond Donors: A Computational Study on the Thiourea–Iodonium System DOI Creative Commons
Alexander S. Novikov, Dmitrii S. Bolotin

Published: April 3, 2023

A computational analysis of possible routes cooperative catalysis involving hydrogen bond (HB) and halogen (XB) donating organocatalysts has been carried out. Previously suggested route including electrophilic activation HB donor by XB was ruled out but a path double reaction electrophile its simultaneous association with the species confirmed DFT calculations.

Language: Английский

Citations

0
Halogen-Bond-Based Organocatalysis Unveiled: Computational Design and Mechanistic Insights DOI Creative Commons
Nika Melnyk, Marianne Rica Garcia, Cristina Trujillo

et al.

Published: Aug. 30, 2023

Halogen-bond-based organocatalysis is a promising alternative to the extensively explored halogen-bond-based catalysis. This paper presents comprehensive theoreti- cal investigation of structural and electronic properties σ-hole, as well computational design series electronically activated monodentate bidentate iodine benzimidazolium achiral donor systems, inspired by experimental com- putational papers published in last decade. The aforementioned activation modes are compared, mechanistic details reaction discussed.

Language: Английский

Citations

0