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

• Published in: Journal of molecular modeling Vol. 30; no. 7; p. 201
• Main Authors: Ferrer, Maxime, Elguero, José, Alkorta, Ibon, Azofra, Luis Miguel
• Format: Journal Article
• Language: English
• Published: Berlin/Heidelberg Springer Berlin Heidelberg 2024; Springer Nature B.V
• Subjects: Activation energy; Adducts; Carbon dioxide; Characterization and Evaluation of Materials; Chemical potential; Chemical reactions; Chemistry; Chemistry and Materials Science; Computer Appl. in Life Sciences; Computer Applications in Chemistry; Coupling; Decomposition reactions; Density functional theory; Distortion; Electron density; Energy gradient; Hydrogen atoms; Interaction models; Minima; Molecular Medicine; Original Paper; Reaction mechanisms; Theoretical and Computational Chemistry; Amine-CO; coupling; Alcohol-CO; Thiol-CO; REG; Density functional theory (DFT)
• ISSN: 1610-2940; 0948-5023; 0948-5023
• DOI: 10.1007/s00894-024-05992-3

Context
A Conceptual DFT (CDFT) study has been carry out to analyse the coupling reactions of the simplest amine (CH
3
NH
2
), alcohol (CH
3
OH), and thiol (CH
3
SH) compounds with CO
2
to form the corresponding adducts CH
3
NHCO
2
H, CH
3
OCO
2
H, and CH
3
SCO
2
H. The reaction mechanism takes place in a single step comprising two chemical events: nucleophilic attack of the non-metallic heteroatoms to CO
2
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.