Insights into the Distinct Behaviors between Bifunctional and Binary Organoborane Catalysts through Terpolymerization of Epoxide, CO2, and Anhydride DOI
Rui Xie, Yuhui Wang, Shuai Li

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(27)

Published: April 22, 2024

Abstract Alkyl borane compounds‐mediated polymerizations have expanded to Lewis pair polymerization, free radical ionic ring‐opening and polyhomologation. The bifunctional organoborane catalysts that contain the acid ammonium or phosphonium salt in one molecule demonstrated superior catalytic performance for polymerization of epoxides copolymerization CO 2 than their two‐component analogues, i.e., blend salt. To explore origin differences one‐component catalysts, here we conducted a systematic investigation on performances these two kinds via terpolymerization epoxide, carbon dioxide anhydride. resultant terpolymers produced independently by binary catalyst exhibited distinct microstructures, where series gradient polyester‐polycarbonate with varying polyester content were afforded using catalyst, while tapering diblock obtained system. enhances competitiveness insertion anhydride, which leads premature incorporation into polymer chains ultimately results formation terpolymers. DFT calculations revealed role electrostatic interaction charge distribution caused intramolecular synergistic effect catalyst.

Language: Английский

Ring-opening Polymerization of Cyclic Esters Mediated by Base/(Thio)urea Binary Catalysts toward Sustainable Polyesters DOI
Liying Wang, Ying‐Ying Liu, Yong Shen

et al.

Polymer Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

The recent advancements in the synthesis of sustainable polyesters mediated by base/(thio)urea binary catalysts are discussed, focusing on catalytic mechanism, activity and selectivity as well current challenges future directions.

Language: Английский

Citations

4
B(MIDA)-directed site-selective intermolecular halofluoroalkylation of alkenes: synthesis of diversely functionalized building blocks DOI Creative Commons
Hengbo Wu, Rong Luo, Jingjing Peng

et al.

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

B(MIDA) dictated Pd-catalyzed halofluoroalkylation of alkenes with fluoroalkyl halides for the synthesis fluorinated α-halo boronates is developed. This unique technique characterized by high efficiency and a remarkably broad substrate scope.

Language: Английский

Citations

0
Organocatalyzed Copolymerization of CO 2 with Epoxide Toward Polycarbonate Synthesis DOI Open Access
Xiaoshuang Feng, Yves Gnanou

Published: March 7, 2025

Language: Английский

Citations

0
Boron Compounds as Key Drivers of Innovation: Exploring Their Role in Environmental Remediation, Sustainable Agriculture, Advanced Biomedical Applications, and Green Chemistry DOI
Metin Yıldırım, Mehmet Erşatır, Mohammed Saleh

et al.

Journal of Organometallic Chemistry, Journal Year: 2025, Volume and Issue: 1035, P. 123688 - 123688

Published: April 28, 2025

Language: Английский

Citations

0
Understanding the Effect of M(III) Choice in Heterodinuclear Polymerization Catalysts DOI Creative Commons
Katharina H.S. Eisenhardt,

Francesca Fiorentini,

Charlotte K. Williams

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 19, 2024

The ring-opening copolymerization (ROCOP) of epoxides with CO2 or anhydrides is a promising strategy to produce sustainable polycarbonates and polyesters. Currently, most catalysts are reliant on scarce expensive cobalt as the active center, while more abundant aluminum iron often suffer from lower activities. Here, two novel heterodinuclear catalysts, featuring Al(III), Fe(III), K(I) centers, synthesized, their performance in polymerization four different monomer combinations compared that Co(III) analogue. Al(III)K(I) catalyst exhibits outstanding activities cyclohexane oxide (CHO)/CO2 ROCOP, at 1 bar pressure it fastest aluminum-based reported date. M(III) site electronics for all three Al(III)K(I), Fe(III)K(I), Co(III)K(I), measured using IR NMR spectroscopy, cyclic voltammetry, single crystal X-ray diffraction. A correlation between electron density catalytic activity revealed and, based established structure–activity relationship, recommendations future design Al(III)- Fe(III)-based made. performances both Fe(III)K(I) further contextualized against relative elemental abundance cost. On balance performance, abundance, cost, complex better carbon dioxide/epoxide preferable anhydride/epoxide ROCOP.

Language: Английский

Citations

2
Synthesis of Heterometallic Rare Earth(III)–Cobalt(II) Complexes and Their Application in Alternating Copolymerization of Cyclohexene Oxide and Carbon Dioxide DOI

Yanping Song,

Kuan Yin,

Yongjie Chen

et al.

Chinese Journal of Chemistry, Journal Year: 2022, Volume and Issue: 41(7), P. 805 - 813

Published: Dec. 7, 2022

Comprehensive Summary Four heterometallic rare earth(III)‐cobalt(II) complexes (rare earth = Y ( 1 ), Sm 2 Nd 3 La 4 )) stabilized by an o ‐phenylenediamine‐bridged tris(phenolato) ligand (L) have been synthesized and characterized. In these tetranuclear complexes, one polydentate L coordinates to earth(III) ion, cobalt(II) respectively, while two ions are bridged four acetate groups. These were applied in the copolymerization of cyclohexene oxide CO , which showed good activity (TON up 440) high poly(cyclohexene carbonate) selectivity (>99%). Kinetic studies determined equation as rate k [CHO] [CO ] 0 [initiator] proves a first‐order dependence on initiator concentrations implies synergistic mechanism with cobalt cooperating epoxide ring‐opening chain propagation.

Language: Английский

Citations

11
Precise Synthesis of Sequence-Controlled Oxygen-Rich Multiblock Copolymers via Reversible Carboxylation of a Commercial Salen-Mn(III) Catalyst DOI
Zhenjie Yang, Chenyang Hu,

Zan Gao

et al.

Macromolecules, Journal Year: 2023, Volume and Issue: 56(6), P. 2370 - 2378

Published: March 15, 2023

The precise synthesis of multiblock copolymers is great significance in polymer chemistry. Switchable polymerization catalysis developed via reversible carboxylation a commercial salen-manganese (Mn) complex. essence was the transition between Mn alkoxide (Mn-OR) and carboxylate (Mn-OCOR). unique toggling mechanism two active species for different pathways applied to chemoselective copolymerization epoxides, anhydrides, LA. anhydrides act as both self-switching agent feedstock polymerization. Needless cocatalyst or chain-transfer (CTA), poly(anhydride-epoxide) segments were situ introduced into PLA chain batches, yielding various novel with control. Theoretical modulations conducted provide robust explanation switching mechanism.

Language: Английский

Citations

5
Self-switchable polymerization catalysis with monomer mixtures: using a metal-free commercial thiourea catalyst to deliver block polyesters DOI
Xue Liang, Wenli Wang, Dan Zhao

et al.

Polymer Chemistry, Journal Year: 2023, Volume and Issue: 14(43), P. 4918 - 4926

Published: Jan. 1, 2023

An easily accessible and cost-effective catalytic system, TU/PPNCl, was developed to produce sequence-controlled multiblock polyesters by self-switchable polymerization from a monomer mixture of epoxides, anhydrides, cyclic esters.

Language: Английский

Citations

5
Monomer-controlled self-switchable polymerization: a metal-free strategy for synthesizing multiblock copolymers from epoxides, O-phthalaldehyde, and CO2 DOI
Qi Zhang,

Mingxin Niu,

Haotian Zhang

et al.

Polymer Chemistry, Journal Year: 2023, Volume and Issue: 14(44), P. 4979 - 4985

Published: Jan. 1, 2023

The preparation of multiblock copolymers is facilitated by monomer-controlled self-switchable terpolymerization.

Language: Английский

Citations

4
A Binary Silicon‐Centered Organoboron Catalyst with Superior Performance to That of Its Bifunctional Analogue DOI Open Access
Cheng‐Kai Xu, Guan‐Wen Yang, Chenjie Lu

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(48)

Published: Oct. 17, 2023

This work reported that a silicon-centered alkyl borane/ammonium salt binary (two-component) catalyst exhibits much higher activity than its bifunctional analogue (one-component) for the ring-opening polymerization of propylene oxide, showing 7.3 times at low loading 0.01 mol %, and even 15.3 an extremely 0.002 %. By using 19 F NMR spectroscopy, control experiments, theoretical calculation we discovered central silicon atom displays appropriate electron density larger intramolecular cavity, which is useful to co-activate monomer deliver propagating chains, thus leading better synergic effect analogue. A unique two-pathway initiation mode was proposed explain unusual high catalytic system. study breaks traditional impression Lewis acid/nucleophilic with poor because increase in entropy.

Language: Английский

Citations

4