Chemical fixation of CO2 with propylene oxide catalyzed by Trimethylsulfonium bromide in the presence of HBr: a computational study

Ali, Jemal Mohamed; Lelisho, Teshome Abute

doi:10.1007/s00214-020-02673-1

Cited by 5 publications

(7 citation statements)

References 46 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The conversion of 3a into 4a via TS2a shows highest activation energy, therefore, it is the slowest step i.e. rate determining step for the reaction [54]. Free energy of activation is also maximum for this conversion.…”

Section: Resultsmentioning

confidence: 99%

Quantum Mechanical Modeling Unveil the Effect of Substitutions on the Activation Barriers of the Diels-Alder Reactions of an Antiviral Compound 7H-Benzo[a]phenalene

Rehman

Mansha

Zahid

et al. 2021

Preprint

View full text Add to dashboard Cite

Density functional theory has been utilized for exploring the mechanism of Diels-Alder reaction between 7H-benzo[a]phenalene and maleic anhydride. 7H-Benzo[a]phenalene is an antiviral compound and information available about its cycloaddition reactions with possible reaction path and mechanism is scarce. In order to work on the synthesis of its further potential derivatives, the mechanism of its reaction with all aspects should be well understood. Two novel intermediates involved in this reaction have been reported. Diels-Alder reaction of maleic anhydride has found many applications in the synthesis of wide range of useful products. The major concern of this work is to evaluate the consequences of introducing electron donating and electron withdrawing substituents on the reactivity of maleic anhydride towards 7H-benzo[a]phenalene. Thermodynamic parameters, activation parameters, energies of frontier orbitals, global reactivity indices and global electron density transfer (GEDT) have been determined for all the reactions. Fukui functions are computed for each reactant in order to identify the most reactive sites. All the reactions have been found to proceed via normal electron demand having polar nature. The substituents with opposite electronic properties were expected to affect the reactivity of dienophile in an inverse manner, however, the results are not according to this assumption. Rather, both kinds of substituents increased the activation barrier of the reaction. This behavior has been explained in the light of various parameters such as the stability of reacting species, gap of frontier molecular orbitals etc. Experimental studies reported previously are in agreement with these results.

show abstract

Section: Resultsmentioning

confidence: 99%

Quantum Mechanical Modeling Unveil the Effect of Substitutions on the Activation Barriers of the Diels-Alder Reactions of an Antiviral Compound 7H-Benzo[a]phenalene

Rehman

Mansha

Zahid

et al. 2021

Preprint

View full text Add to dashboard Cite

show abstract

“…For an uncatalyzed reaction system the transition state needs Gibbs free energy activation of ΔG = 63.69 kcal/mol in the gas phase at 298.15 K and 1 atm which is in good agreement with previous reports. 18,23,30 The high activation energy for the uncatalyzed reaction S C H E M E 1 Synthesis of propylene carbonate from carbon dioxide and propylene oxide explains the very high temperature required to perform this reaction without a catalyst. Therefore, the use of a catalyst is crucial to lowering this activation barrier.…”

Section: Coupling Without Catalystmentioning

confidence: 99%

“…In a previous report, it was found that the unsubstituted carbon atom of PO is the electrophilic center, as compared to the methyl substituted carbon atom of PO. 30…”

Section: Coupling With Catalystmentioning

confidence: 99%

“…Using suitable cocatalysts such as KI, 52 LiBr, 51 and HBDs, the catalytic activity of ILs can be dramatically increased, as proven in various theoretical research, It works by (i) interacting with the O-donor group of epoxides, facilitating ring-opening by the nucleophilic attack of the halide counter-anion of the salt or IL, and (ii) stabilizing the oxyanion formed after the epoxide ring-opening step by hydrogen bonding or jointing with the cation of the salt. 30,46,48 A binary catalytic system is often required to get good conversions/yields under mild reaction conditions and to decrease the large energy barriers seen in the ringopening process, as discussed extensively in the literature. 21 A Lewis acid and a suitable nucleophile are frequently used in a binary catalytic system to make the ring-opening step-less energetically demanding and the subsequent CO 2 insertion easier.…”

Section: Catalyzed By (Ch 3 ) 4 Piámgclmentioning

confidence: 99%

“…29 Despite the study most of the catalyst systems are toxic, expensive, or involve using organic solvents. [30][31][32][33][34] In the study, we have for the first time investigated computationally the coupling reaction between propylene oxide (PO) and CO 2 by using (CH 3 ) 4 PIÁMgCl 2 as a catalyst in mild reaction conditions.…”

mentioning

confidence: 99%

See 2 more Smart Citations

Mechanistic study on the coupling reaction of CO₂ with propylene oxide catalyzed by (CH₃)₄PI·MgCl₂

2022

Self Cite

View full text Add to dashboard Cite

The mechanistic study of CO2 coupling with propylene oxide (PO) into cyclic carbonate catalyzed by (CH3)4PI has been investigated using the B3LYP/6‐311++G (d, p)/B3LYP/6‐31G (d) level of theory for non‐iodine atoms and LANL2DZ was used, together with its associated basis set for the iodine atom. Two hypothetical reaction mechanisms were proposed for the studied reaction and thermodynamic and kinetic parameters were computed for each step to determine the more favorable route. The density functional theory (DFT) study reveals that the reaction prefers to proceed through a three‐step mechanism (pathway II) than a tri‐molecular intermediate (pathway I) where the CO2 and the catalyst act simultaneously on the PO ring. The rate‐determining step of the catalytic reaction is found to be the ring‐opening step with an energy barrier of 27.1 kcal/mol (pathway II) in the gas phase, which is kinetically more favorable than that of non‐catalytic CO2 fixation with a relatively higher barrier of 63.7 kcal/mol. The synergetic effect of MgCl2 is tested as a cocatalyst for the (CH3)4PI/MgCl2 catalyzed reaction and it gave a better result and minimized the activation energy for the reaction and the rate‐determining step was the ring closure with the free energy of activation 18.8 kcal/mol in the gas phase. The polarizable continuum model was used to account for the solvent effect, obtaining the best results of 23.1 kcal/mol in water for pathway I and 16.5 kcal/mol and 14.9 kcal/mol in dimethyl sulfoxide for pathway II and binary system, respectively.

show abstract

Synthesis and computational studies for halide‐free, neutral, and bifunctional one‐component ferrocene‐based catalysts for the coupling of carbon dioxide and epoxides

Lee,

Kim

et al. 2024

Bulletin Korean Chem Soc

View full text Add to dashboard Cite

We used stable and nontoxic [(dimethylamino)methyl]ferrocene (Fc‐N), (hydroxymethyl)ferrocene (Fc‐O), 1,2‐bis[(dimethylamino)methyl]ferrocene (Fc‐N2), and 1‐[(dimethylamino)methyl]‐2‐(hydroxymethyl)ferrocene (Fc‐NO) as halide‐free, neutral, and bifunctional one‐component catalysts for the synthesis of cyclic carbonates. They do not need halide‐based additives or tethered salts attached to ligands when used for this coupling reaction. Among them, Fc‐N2 exhibited the best catalytic activity under the same reaction conditions. Catalytic activity decreased rapidly in the order Fc‐N2 > Fc‐NO > Fc‐N > Fc‐O, and interestingly, the more amino groups introduced into the Cp groups, the higher the activity. Various terminal and internal epoxides were easily converted into the corresponding cyclic carbonates. Calculations based on the density functional theory were also carried out to elucidate the mechanism of the coupling reaction.

show abstract

Chemical fixation of CO2 with propylene oxide catalyzed by Trimethylsulfonium bromide in the presence of HBr: a computational study

Cited by 5 publications

References 46 publications

Quantum Mechanical Modeling Unveil the Effect of Substitutions on the Activation Barriers of the Diels-Alder Reactions of an Antiviral Compound 7H-Benzo[a]phenalene

Quantum Mechanical Modeling Unveil the Effect of Substitutions on the Activation Barriers of the Diels-Alder Reactions of an Antiviral Compound 7H-Benzo[a]phenalene

Mechanistic study on the coupling reaction of CO₂ with propylene oxide catalyzed by (CH₃)₄PI·MgCl₂

Synthesis and computational studies for halide‐free, neutral, and bifunctional one‐component ferrocene‐based catalysts for the coupling of carbon dioxide and epoxides

Contact Info

Product

Resources

About

Chemical fixation of CO2 with propylene oxide catalyzed by Trimethylsulfonium bromide in the presence of HBr: a computational study

Cited by 5 publications

References 46 publications

Quantum Mechanical Modeling Unveil the Effect of Substitutions on the Activation Barriers of the Diels-Alder Reactions of an Antiviral Compound 7H-Benzo[a]phenalene

Quantum Mechanical Modeling Unveil the Effect of Substitutions on the Activation Barriers of the Diels-Alder Reactions of an Antiviral Compound 7H-Benzo[a]phenalene

Mechanistic study on the coupling reaction of CO2 with propylene oxide catalyzed by (CH3)4PI·MgCl2

Synthesis and computational studies for halide‐free, neutral, and bifunctional one‐component ferrocene‐based catalysts for the coupling of carbon dioxide and epoxides

Contact Info

Product

Resources

About

Mechanistic study on the coupling reaction of CO₂ with propylene oxide catalyzed by (CH₃)₄PI·MgCl₂