Theoretical rate constant of methane oxidation from the conventional transition-state theory

Aranda, Claudia Alejandra Sánchez; Richaud, Arlette; Méndez, Francisco; Domı́nguez, Armando

doi:10.1007/s00894-018-3829-y

Cited by 4 publications

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“…The water increased the yield of 3a by 11% and decreased the time and temperature of the reaction by Δ T = 40 °C and Δ t = 0.5 h. According to the reaction mechanism, the rate-determining (rate-controlling) step of the reaction is the formation of TS1 (see Scheme and Figure ). Using the conventional transition theory, , we calculated the rate constant k for the reaction in the absence of DES and H 2 O (red line, Figure ), the k (DES) for the reaction in the presence of DES (blue line, Figure ), and the k (DES/H2O) for the reaction in the presence of DES/H 2 O (green line, Figure ). The ratio of reaction rates showed the trend {[ k (DES/H2O) / k ] = 28.998 × 10 11 } > {[ k (DES) / k ] = 2.305 × 10 11 } ≫ {[ k / k ] = 1}.…”

Section: Results and Discussionmentioning

confidence: 99%

Deep Eutectic Solvent Choline Chloride/p-toluenesulfonic Acid and Water Favor the Enthalpy-Driven Binding of Arylamines to Maleimide in Aza-Michael Addition

et al. 2020

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Deep eutectic solvents (DESs) have been considered "the organic reaction medium of the century" because they can be used as solvents and active catalysts in chemical reactions. However, experimental and theoretical studies are still needed to provide information on the structures of DESs, the kinetics and thermodynamics properties, the interactions between the DESs and the substrates, the effect of water on the DES supramolecular network and its physicochemical properties, and so forth. This information is very useful to understand the essence of the processes that take place in the catalysis of chemical reactions and, therefore, to help in the design of a DES for a specific reaction and sample. This article shows a systematic study of the impact of DES choline chloride/p-toluenesulfonic acid and DES choline chloride/ p-toluenesulfonic acid−water in the aza-Michael addition of arylamines to maleimide to obtain aminopyrrolidine-2,5-dione derivatives. The derivatives are obtained under very mild reaction conditions with good yield. The global reaction is exothermic, spontaneous, permitted by enthalpy, and prohibited for entropy. The calculated potential energy surface shows a reaction mechanism of six steps controlled by enthalpy (except the last step that is controlled by entropy). The water incorporated in the supramolecular DES complex stabilizes the transition states and favors the enthalpy-driven binding. A set of H/D exchange NMR experiments validates the transition state existing in the fourth stage of the mechanism.

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Section: Results and Discussionmentioning

confidence: 99%