Topological investigation of the reaction mechanism of glycerol carbonate decomposition by bond evolution theory

Adjieufack, Abel Idrice; Liégeois, Vincent; Ndassa, Ibrahim Mbouombouo; Champagne, Benoı̂t

doi:10.1039/d0ra09755a

Cited by 14 publications

(9 citation statements)

References 53 publications

(55 reference statements)

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“…However, the key questions that must be addressed to understand the nature of the molecular mechanisms remain related to fundamental chemistry: the distribution and the evolution of electron density along the reaction pathway. The bonding evolution theory, based on the changes described by Thom's catastrophe theory on the electron localization function topology along a given reaction path, is capable of unambiguously identifying the main chemical events happening throughout chemical reactions, [35–40] and generating the corresponding curly arrows to describe the reaction mechanism [41,42] …”

Section: Introductionmentioning

confidence: 99%

Exploring The Sequence of Electron Density Along The Chemical Reactions Between Carbonyl Oxides And Ammonia/Water Using Bond Evolution Theory

et al. 2021

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The molecular mechanism of the reactions between four carbonyl oxides and ammonia/water are investigated using the M06‐2X functional together with 6‐311++G(d,p) basis set. The analysis of activation and reaction enthalpy shows that the exothermicity of each process increased with the substitution of electron donating substituents (methyl and ethenyl). Along each reaction pathway, two new chemical bonds C−N/C−O and O−H are expected to form. A detailed analysis of the flow of the electron density during their formation have been characterized from the perspective of bonding evolution theory (BET). For all reaction pathways, BET revealed that the process of C−N and O−H bond formation takes place within four structural stability domains (SSD), which can be summarized as follows: the depopulation of V(N) basin with the formation of first C−N bond (appearance of V(C,N) basin), cleavage of N−H bond with the creation of V(N) and V(H) monosynaptic basin, and finally the V(H,O) disynaptic basin related to O−H bond. On the other hand, in the case of water, the cleavage of O−H bond with the formation of V(O) and V(H) basins is the first stage, followed by the formation of the O−H bond as a second stage, and finally the creation of C−O bond.

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Section: Introductionmentioning

confidence: 99%

Exploring The Sequence of Electron Density Along The Chemical Reactions Between Carbonyl Oxides And Ammonia/Water Using Bond Evolution Theory

et al. 2021

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“…From the analysis of the electron density, which is measurable from the experimental point of view, the BET associating the ELFs , and Thom’s catastrophe theory has become a new tool for the study of the electronic reorganizations (bond breaking/formation) occurring along the chemical reactions. − Hence, many reaction mechanisms have been studied in the framework of BET. Here, we carried out this BET analysis along the exo -approach for the 32 CA reactions between NPPN 1a , NtBPN 1b , and STY 2 .…”

Section: Results and Discussionmentioning

confidence: 99%

How a Chromium Tricarbonyl Complex Catalyzes the [3 + 2] Cycloaddition Reaction of N-Substituted Phenylnitrones with Styrene: A Molecular Electron Density Theory Analysis

et al. 2022

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The reaction mechanisms of [3 + 2] cycloaddition (32CA) between two N-substituted phenylnitrones (NPPN and NtBPN) and styrene (STY) in the presence of a chromium tricarbonyl complex (Cr(CO)3) have been studied within the framework of molecular electron density theory at the MPWB1K/6-311G(d,p) level. Activation energy analysis reveals that these 32CA reactions take place with high activation barriers due to their non-polar character and with the exo/ortho approach as a favorable reaction path. The activation energy of TS1 series (NPPN) is about 5–6 kcal/mol lower than that of the TS2 series (NtBPN), due to the steric hindrance of tert-butyl at the TS2 structures. Coordination of chromium tricarbonyl to each reactant to form the corresponding complex slightly increases the nucleophilic and electrophilic character of NPPN:Cr, NtBPN:Cr, and STY:Cr, which can be considered a strong nucleophile and electrophile able to participate in a polar 32CA reaction. This polar character in the presence of the chromium tricarbonyl complex was verified by the higher (up to 0.20e) values of global electron density transfer for Cr(CO)3-coordinated transition states. Electron localization function analysis along the exo/ortho reaction path reveals the non-concerted mechanism in the formation of a new bond with the initial appearance of a C–C single bond followed by the O–C one.

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“…14 A bit later, by combining ELFs 14 with Thom's catastrophe, 15 Krokidis and Silvi developed the Bonding Evolution Theory (BET), 16,17 which, over the years, has been demonstrated to have irrevocable robustness in unraveling the chemical bond-breaking and -forming processes in a diversity of organic synthesis mechanisms. [18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36] Benzothiazole is a molecule of interest. It belongs to one of the most important classes of heterocyclic compounds, and it plays a significant role in medicinal chemistry.…”

Section: Paper Synthesismentioning

confidence: 99%

Investigating the Mechanism of the Catalytic Intramolecular Aza-Wittig Reaction Involved in the Synthesis of 2-Methylbenzothiazole from the Perspective of Bonding Evolution Theory

2023

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The Bonding Evolution Theory has been used at the Density Functional Theory level [ωB97X-D exchange-correlation functional, 6-311G(d,p) basis set, and solvent (toluene) effects with polarizable continuum model] to unravel the reaction mechanism of the intramolecular aza-Wittig reaction of 2-(acetylthio)phenyl isocyanate (1) catalyzed by 3-methyl-1-phenyl-2-phospholene 1-oxide (2) to form 2-methylbenzothiazole (3). The reaction involves four steps (transition states) corresponding to i) the formation of a cycloadduct (O-C then P-N bonds), ii) then a decarboxylation leading to the formation of an iminophosphorane, and iii) an intramolecular [2+2] cycloaddition (N-C then P-O bonds) followed by iv) a retro [2+2] cycloaddition (cleavage of the P-N then O-C bonds) to get the product and regenerate the catalyst. Step 1 is the rate determining step with an activation Gibbs free enthalpy of 21 kcal mol-1 and it is favored with respect to a competitive pathway leading to the formation of another cycloadduct (P-C then O-N bonds). The whole reaction is exergonic with a Gibbs free energy decrease of 31 kcal mol-1, associated with the liberation of a CO2 molecule and the formation of the aromatic benzothiazole. Following the scale of Domingo, the successive steps of the reaction have a polar nature.

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Topological investigation of the reaction mechanism of glycerol carbonate decomposition by bond evolution theory

Abstract: ELFs of glycerol carbonate and of its kinetic and thermodynamic decomposition product, 3-hydroxypropanal (+CO2).

Cited by 14 publications

References 53 publications

Exploring The Sequence of Electron Density Along The Chemical Reactions Between Carbonyl Oxides And Ammonia/Water Using Bond Evolution Theory

Exploring The Sequence of Electron Density Along The Chemical Reactions Between Carbonyl Oxides And Ammonia/Water Using Bond Evolution Theory

How a Chromium Tricarbonyl Complex Catalyzes the [3 + 2] Cycloaddition Reaction of N-Substituted Phenylnitrones with Styrene: A Molecular Electron Density Theory Analysis

Investigating the Mechanism of the Catalytic Intramolecular Aza-Wittig Reaction Involved in the Synthesis of 2-Methylbenzothiazole from the Perspective of Bonding Evolution Theory

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