Theoretical study of the formation of pyrazole and indazole carbamic acids

Ferrer, Maxime; Alkorta, Ibon; Elguero, Jose

doi:10.1007/s11224-024-02286-5

Cited by 4 publications

(1 citation statement)

References 84 publications

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“…The CO 2 absorption by amine solutions, specially monoethanolamine (MEA) [ 31 – 34 ], is frequently used industrially. Also, supported amines [ 34 – 37 ] and nitrogen heterocycles are capable of react with CO 2 [ 38 ]. In general, this reaction processess with the formation of the carbamic acid followed in some cases by deprotonation to yield the corresponding carbamate [ 39 – 41 ].…”

Section: Introductionmentioning

confidence: 99%

Understanding the coupling of non-metallic heteroatoms to CO2 from a Conceptual DFT perspective

Ferrer,

Elguero,

Alkorta

et al. 2024

J Mol Model

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Context A Conceptual DFT (CDFT) study has been carry out to analyse the coupling reactions of the simplest amine (CH3NH2), alcohol (CH3OH), and thiol (CH3SH) compounds with CO2 to form the corresponding adducts CH3NHCO2H, CH3OCO2H, and CH3SCO2H. The reaction mechanism takes place in a single step comprising two chemical events: nucleophilic attack of the non-metallic heteroatoms to CO2 followed by hydrogen atom transfer (HAT). According to our calculations, the participation of an additional nucleophilic molecule as HAT assistant entails important decreases in activation electronic energies. In such cases, the formation of a six-membered ring in the transition state (TS) reduces the angular stress with respect to the non-assisted paths, characterised by four-membered ring TSs. Through the analysis of the energy and reaction force profiles along the intrinsic reaction coordinate (IRC), the ratio of structural reorganisation and electronic rearrangement for both activation and relaxation energies has been computed. In addition, the analysis of the electronic chemical potential and reaction electronic flux profiles confirms that the highest electronic activity as well as their changes take place in the TS region. Finally, the distortion/interaction model using an energy decomposition scheme based on the electron density along the reaction coordinate has been carried out and the relative energy gradient (REG) method has been applied to identify the most important components associated to the barriers. Methods The theoretical calculation were performed with Gaussian-16 scientific program. The B3LYP-D3(BJ)/aug-cc-pVDZ level was used for optimization of the minima and TSs. IRC calculations has also been carried out connecting the TS with the associated minima. Conceptual-DFT (CDFT) calculations have been carried out with the Eyringpy program and in-house code. The distortion/interaction model along the reaction coordinate have used the decomposition scheme of Mandado et al. and the analysis of the importance of each components have been done with the relative energy gradient (REG) method.

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Section: Introductionmentioning

confidence: 99%

Understanding the coupling of non-metallic heteroatoms to CO2 from a Conceptual DFT perspective

Ferrer,

Elguero,

Alkorta

et al. 2024

J Mol Model

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Low Valence Triel (I) Systems as Hydrogen Bond Acceptors and their Stability with Respect to Triel (III) Compounds

Sánchez‐Sanz,

Alkorta,

Elguero

2024

ChemPhysChem

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A theoretical study of the complexes formed by carbene like Al(I), Ga(I), In(I) and Tl(I) compounds with hydrogen bond donors (HBD), XH (HCCH, HSH ,HOH, HCN, HCl, HBr, HF, and HNC) have been carried out at MP2 computational level. The isolated triel(I) compounds show a negative region of the molecular electrostatic potential region associated with the triel atom suitable to interact with electron deficient groups. This region is associated to a lone pair based on the ELF analysis and to the location of the HOMO orbital. The complexes are similar to those found in nitrogen heterocyclic carbenes (NHC) with HBD. In addition, the oxidative addition reactions of those complexes to yield the corresponding valence III compounds have been characterized. The Al(III) compounds are much more stable than the corresponding Al(I) complexes. However, the stability of the triel(III) compounds decreases with the size of the triel atom and for the thallium derivatives, the Tl(I) complexes are more stable than the Tl(III) compounds in accordance with the number of the structures found in the CSD. The barrier of the TS connecting the triel(I) and triel(III) systems increases with the size of the triel atoms.

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Intramolecular hybrid diamine DMAPA/n-PeOH/H2O biphasic absorbent for CO2 absorption through combining zwitterion and base-catalyzed hydration mechanism

Wang,

Yang,

Guo

et al. 2024

Chemical Engineering Science

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Theoretical study of the formation of pyrazole and indazole carbamic acids

Cited by 4 publications

References 84 publications

Understanding the coupling of non-metallic heteroatoms to CO2 from a Conceptual DFT perspective

Understanding the coupling of non-metallic heteroatoms to CO2 from a Conceptual DFT perspective

Low Valence Triel (I) Systems as Hydrogen Bond Acceptors and their Stability with Respect to Triel (III) Compounds

Intramolecular hybrid diamine DMAPA/n-PeOH/H2O biphasic absorbent for CO2 absorption through combining zwitterion and base-catalyzed hydration mechanism

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