Amine–MeOH Binary Systems as Catalysts for Cyclic Carbonate Formation from Epoxides and Carbon Dioxide: A DFT Mechanistic Investigation

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 8, 2025

The detailed mechanism of propylene carbonate (PC) formation from oxide (PO) and CO2 is investigated using density functional theory (DFT) methods, catalyzed by amine/MeOH binary systems, in under conditions room temperature 1 atm. In these amines (MeNH2, Me2NH, Me3N, pyrrolidine) serve as nucleophiles, while MeOH acts a hydrogen bond donor (HBD). reaction pathways for PC consistently proceed through two transition states, ts1 ts2, corresponding to the ring-opening final ring-closing steps, respectively. step was identified rate-determining all systems. Notably, three aliphatic systems significantly lower activation barriers approximately 20 kcal mol-1 compared uncatalyzed pathway standard conditions. Me2NH/MeOH system demonstrates slightly higher catalytic efficiency than MeNH2 Me3N Furthermore, pyrrolidine/MeOH exhibits comparable performance system. Since pyrrolidine liquid conditions, it can act homogeneous catalyst when paired with MeOH, enhancing mixing PO improving activity relative gaseous Me2NH.

Language: Английский

---

High-resolution 3D printable inks based on functional polymeric ionic liquids for applications in carbon dioxide valorization

Additive manufacturing, Journal Year: 2024, Volume and Issue: 89, P. 104304 - 104304

Published: June 1, 2024

This study investigates the use of epoxy-functionalized acrylate-based 3D printable ink for creating high-resolution functionalized devices, exploring possibility to further functionalize those chemical engineering applications. In fact, control surface enables formation active surfaces, and this employs supported Ionic Liquids with catalytic properties as a proof concept. liquids (ILs) polymeric derivatives represent promising path generate multifunctional complex structures, playing advanced roles in multiple The fine-tuning functionalization methodology formulation enhances resolution resins, allowing production highly detailed structures that can significantly boost efficiency. Through comparison commercial developed demonstrates superior capabilities, positioning it an effective alternative vat photopolymerization technologies. Additionally, controlling level accessibility ILs' sites through area reactor has led improved process performance terms yield space-time (STY) CO2 cycloaddition epoxide reaction.

Language: Английский

---

Poly(ionic liquid)-based aerogels for continuous-flow CO2 upcycling

Journal of CO2 Utilization, Journal Year: 2024, Volume and Issue: 83, P. 102771 - 102771

Published: April 23, 2024

The atmospheric concentration of CO2 is rising at an alarming pace, creating a pressing need for new and sustainable materials capable capture conversion. Poly(ionic liquid)s (PILs) are particularly effective catalysts processes or near pressure. PILs industrial application poses challenges due to the low porosity PIL, limited batch conversion capacity, difficulties in reuse. To overcome these limitations, we herein propose use AEROPILs obtained from integration chitosan-based aerogels. These cost-effective highly porous have unique tuneable properties making them not only ideal sorbents but also promising heterogeneous catalysts. While show moderate yields mode, high catalytic activity was achieved when were used catalyse cycloaddition reaction epoxides packed-bed reactors operated under continuous flow. stability maintained over 60 h without loss, productivity (space-time yield 21.18 gprod h−1 L−1). This research reveals pioneering efficiently upcycle into cyclic carbonate flow setup.

Language: Английский

---

Exploitation of Mechanistic Product Selectivity for the Two‐Step Synthesis of Optically Active Bio‐Derived Cyclic Carbonates Incorporating Amino Acids

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(21)

Published: March 6, 2024

Abstract The synthesis of bio‐derived cyclic carbonates is attracting a lot attention as the incorporation functionality into these compounds provides opportunity to prepare previously unknown structures, whilst also improving their sustainability profiles. This study presents facile preparation diastereomerically pure displaying range optical rotation values. These are obtained from glycidol, amino acids and CO 2 in two‐step approach. Initially, acid functionalised epoxides prepared through robust Steglich esterification enantiopure glycidol ( R or S ) an D L ). Thereafter, second step, cycloaddition epoxide with results retention initial stereochemistry epoxide, furnishing novel optically active carbonate products. A DFT has explained basis this observed configuration for compounds. Further, provide new mechanistic information concerning co‐catalyst‐free reaction starting when using gallium‐catalyst, which found operate metal‐ligand cooperativity.

Language: Английский

---

The Catalytic Coupling of CO₂ and Glycidol toward Glycerol Carbonate

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(16), P. 12454 - 12493

Published: Aug. 5, 2024

Ambitious environmental objectives have driven research and innovation toward the production of biorenewable chemicals, such as glycerol carbonate. In particular, carbonate from coupling CO2 glycidol has received considerable attention chemistry chemical engineering communities. This route became particularly appealing considering that is an activated derivative glycerol, which, together with CO2, industrial waste. To keep chain value high value-added attractive possible, numerous metal-based organo-catalysts been developed. We provide this review a pragmatic overview most promising catalytic protocols reported over past 8 years. Special given to inherent mechanistic structure-(re)activity features key parameters driving reaction performances. also addresses preparation selection catalysts, well global efficiency sustainability Such holistic intended feed inspiration for future highly efficient systems.

Language: Английский

---

Epoxide/CO₂ Cycloaddition Reaction Catalyzed by Indium Chloride Complexes Supported by Constrained Inden Schiff‐Base Ligands

ChemPlusChem, Journal Year: 2023, Volume and Issue: 88(12)

Published: Oct. 10, 2023

Cyclic carbonates have received significant interests for uses as reagents, solvents, and monomers. The coupling reaction of epoxides with carbon dioxide (CO2 ) to produce cyclic carbonate is an attractive route which can significantly reduce greenhouse gas emissions environmental hazards. Herein, a series five indium chloride complexes supported by inden Schiff-base ligands were reported along four X-ray crystal structures. constrained five-membered rings added the enhance coordination In metal. From catalyst screening, complex having tert-butyl substituents propylene backbone in combination tetrabutylammonium bromide (TBAB) exhibited highest catalytic activity (TON up 1017) oxide/CO2 >99 % selectivity under solvent-free conditions. addition, was shown be active at atmospheric pressure CO2 room temperature. system applied various internal terminal epoxide substrates exclusively corresponding carbonates.

Language: Английский

---

Porous organic polymer containing Tröger’s base skeleton and crown ether for cycloaddition of CO2 and efficient iodine vapor adsorption

Journal of Industrial and Engineering Chemistry, Journal Year: 2023, Volume and Issue: 133, P. 482 - 497

Published: Dec. 17, 2023

Language: Английский

---

Chemical CO2 fixation by cyanido bridged heterometallic Zn(II)-Mn(II) 2D coordination polymer

Dalton Transactions, Journal Year: 2024, Volume and Issue: 53(36), P. 15246 - 15257

Published: Jan. 1, 2024

A new cyanido bridged Zn(II)-Mn(II) mixed-metal coordination polymer, {[Zn(μ-L)(μ-CN)

Language: Английский

---

Rational Assembly of Three‐component Coordination Polymers as Heterogeneous Catalysts for CO2 Cycloaddition and Cyanosilylation Reactions

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 7, 2024

Abstract Four new coordination polymers based on 5‐(((1 H ‐imidazol‐2‐yl)methyl)amino) isophthalic acid (H 3 L ) and auxiliary ligands (1,10‐phenanthroline, 2,2′‐bipyridine, 4,4′‐bipyridine), namely, {[Zn(H )(phen)(H 2 O)] ⋅ 2H O} n ( CP 1 ), {[Ni(H O)]} )(2,2′‐bpy)(H {[Cd(H )(4,4′‐bpy) 0.5 4 were rationally assembled. Furthermore, these four CPs screened as heterogeneous catalysts for CO cycloaddition cyanosilylation reactions under mild conditions. The catalytic experiments showed that had the better performance, excellent substrate tolerance recyclability above two reactions. It is speculated activity of may be due to open Lewis base site acidic characteristics zinc (II) center. After five cycles, activities did not significantly decrease, structures remained unchanged. Therefore, was considered efficient stable

Language: Английский

---

Green Conversion of Epoxides to Cyclic Carbonates by Copper Nanocrystals Fabricated on Jute Tartaric Acid Composite Surface

Crystal Research and Technology, Journal Year: 2024, Volume and Issue: 59(11)

Published: Oct. 8, 2024

Abstract The synthesis of copper nanocrystals on tartaric acid jute composite surface is reported. formation detected by FT IR, Powder X‐ray diffraction, SEM, and TEM analysis. average size the found to be 500 nm. reaction with CO 2 resulted in a decrease nanoparticles. Cycloaddition epoxides cyclic carbonate efficiently carried out (CUNPJT) without using any cocatalyst solvent. To best author's knowledge, this first example catalyzing cycloaddition epoxide.

Language: Английский

---