Understanding the mechanism, thermodynamic and kinetic features of the Kukhtin–Ramirez reaction in carbamate synthesis from carbon dioxide

Sabet‐Sarvestani, Hossein; Izadyar, Mohammad

doi:10.1039/c6ra25769k

Cited by 15 publications

(8 citation statements)

References 45 publications

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“…Intrinsic reaction coordinate (IRC) calculations were conducted to ensure that the transition states connected the original reactants and products. 28,29 Comparison of the calculated rate constants with experimental data also provided condence that the prereactant complexes and transition states determined were adequate. The implicit solvation model based on density (SMD) was adopted to investigate the effects of water solvent on the reaction (the dielectric constant was taken to be 78.3553 for water).…”

Section: Methodsmentioning

confidence: 88%

Reactions of hydroxyl radicals with benzoic acid and benzoate

Visscher

Gates

2017

RSC Adv.

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Density functional theory was used to study the mechanism and kinetics of benzoic acid with hydroxyl radicals in both gas and aqueous phases as well as benzoate with hydroxyl radicals in the aqueous phase at the M06-2X/6-311+G(d,p) level of theory. The results show that all reaction pathways involved the formation of pre-reactive complexes which in turn alter reaction energy barriers. The reaction rate constants, calculated based on classical transitional theory, followed the order of meta addition > para addition > ortho addition for the reaction of benzoic acid and hydroxyl radicals in both gas and aqueous media. The energy barrier analysis reveals that the ortho adducts were also less vulnerable to subsequent reaction. In addition, the rate constants for the addition reactions were highest for benzoate in the aqueous phase, followed by benzoic acid in the aqueous phase, then by benzoic acid in the gas phase, consistent with electrostatic potential analysis. However, the rate constants of hydrogen abstraction in the aqueous phase were much lower than that in the gas phase and thus, gas phase reactions are preferred. The incorporation of one explicit water molecule, for addition reactions between benzoic acid and hydroxyl radicals, lowered reaction rates in the aqueous phase by increasing the bond length between the oxygen and reacting carbon in the benzene ring. rsc.li/rsc-advances 35776 | RSC Adv., 2017, 7, 35776-35785 This journal is Scheme 1 Reaction pathways of BA and BZ with hydroxyl radicals. (a) Reaction pathways of BA with hydroxyl radicals. (b) Reaction pathways of BZ with hydroxyl radicals. This journal is a Note: units for gas phase rate constants and aqueous phase rate constants are cm 3 per molecule per s À1 , and M À1 s À1 , respectively. 35782 | RSC Adv., 2017, 7, 35776-35785 This journal is

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Section: Methodsmentioning

confidence: 88%

Reactions of hydroxyl radicals with benzoic acid and benzoate

Visscher

Gates

2017

RSC Adv.

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“…[83] With respect to the intermolecular systems stabilized through the hydrogen bond formation, the B2PLYP, B3LYP, and ωB97X-D approaches have also provided very promising results. [84] In some cases, the pure functionals such as MPWB95 have been successfully used, [85] specially in studies of cubic molecules, but not cubane or prismane, actually the polyhedral fullerene. [86] As a matter of fact, despite the MPWB95 has been efficiently tested and approved in studies of noncovalent dimers, [87] molecules containing noble-gases, [88] or even intramolecular π-stacked structures, [89] the intermolecular condition to be described through the use of pure functionals is always a challenging task.…”

Section: Computational Approaches and Quantum Electronic Structure mentioning

confidence: 99%

The definitive challenge of forming uncommon pseudo‐π···H–F and C···H–F hydrogen bonds on cyclic and cubic nonpolar hydrocarbons

Santos

Carvalho

Oliveira

et al. 2020

J of Physical Organic Chem

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Due to the high symmetry and low polarity of the cyclopropane (C 3 H 6), cyclobutane (C 4 H 8), prismane (C 6 H 6), and cubane (C 8 H 8), it is widely known that these structures unlikely act as proton receptors to form intermolecular interactions with monoprotic acids, such as the hydrogen fluoride. Although the C 3 H 6 ÁÁÁHF, C 4 H 8 ÁÁÁHF, C 6 H 6 ÁÁÁHF, and C 8 H 8 ÁÁÁHF are weakly bound complexes, in this current work, all of them were definitively certified on the basis of a theoretical analysis. In according with the structural parameters and spectroscopy modes appraised through the density-functional theory calculations, the more accentuated perturbations are manifested in the hydrogen fluoride. The new hydrogen bond forms framed as pseudo-πÁÁÁH and CÁÁÁH were unveiled through the calculations of the quantum theory of atoms in molecules and natural bond orbital. In this context, the knowledge about the nature of these hydrogen bonds is necessary, wherein it used the symmetry-adapted perturbation theory for computing the contributions of the electrostatic, polarization, exchange, dispersion, and charge transfer terms. Lastly, the practical behavior of these hydrocarbons under the condition to form intermolecular interactions was examined by taking into account the solvent effect with calculations of the polarizable continuum model.

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“…The aryne functional groups have undeniable effects on the CO 2 incorporation. Here, based on the previous experiences [35][36][37][38][39][40], a comprehensive mechanism study was performed on the benzoxazinone formation, consists of two separate routes for the reaction progress. According to the obtained theoretical results at two computational levels, meta and para positions on the arynes have different behaviors against CO 2 or imines.…”

Section: Introductionmentioning

confidence: 99%

Substituent effects and Mechanism Studies in CO2 Transformation to Benzoxazinone Derivatives as Worthwhile N-containing Heterocycles: insight from DFT simulation

Izadyar¹,

Sabet‐Sarvestani²

2021

Preprint

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Investigation of CO2 transformation into value-added organic molecules is an interesting purpose in scientific communities. Here, the substitute effect exploration in CO2 incorporation reaction toward benzoxazinones formation, as a bioactive heterocyclic compound, is the main studied issue. A profound understanding of the substituent effect is helpful toward the investigation of the kinetic and thermodynamic aspects of the reaction. The substituted arynes, an imine compound, and atmospheric CO2 have been reported as the starting reactants. The substituted functional groups show substantial consequences on the studied mechanisms. The obtained results show that mechanism A, in which the imine compound is added as a nucleophile to arynes, is the most probable mechanism. The Energetic Span Model (ESM) was used in the kinetic studies, which indicates the turnover-frequency determining intermediate (TDI) and turnover-frequency determining transition state (TDTS) in the reaction progress. Also, Electron localization function (ELF) analyses reveal that the electron density of a developing monosynaptic basin on the carbon atom (V(C)) at the transition state shows a good linear correlation with the calculated energy values of TDTS. Electron-withdrawing and electron-releasing characters of the substituents have the main effects on the electron density of the developing basin at the transition states which change the TDTS energies.

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Understanding the mechanism, thermodynamic and kinetic features of the Kukhtin–Ramirez reaction in carbamate synthesis from carbon dioxide

Abstract: In this article, thermodynamic and kinetic aspects of the Kukhtin–Ramirez reaction of the carbamate formation from carbon dioxide have been investigated in the presence of various phosphorous reagents (PRs), theoretically.

Cited by 15 publications

References 45 publications

Reactions of hydroxyl radicals with benzoic acid and benzoate

Reactions of hydroxyl radicals with benzoic acid and benzoate

The definitive challenge of forming uncommon pseudo‐π···H–F and C···H–F hydrogen bonds on cyclic and cubic nonpolar hydrocarbons

Substituent effects and Mechanism Studies in CO2 Transformation to Benzoxazinone Derivatives as Worthwhile N-containing Heterocycles: insight from DFT simulation

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