Mañana, JUEVES, 24 DE ABRIL, el sistema se apagará debido a tareas habituales de mantenimiento a partir de las 9 de la mañana. Lamentamos las molestias.
Dramatic efect of the nature of R on the intrinsic acidity and basicity of potential astrochemical R–C≡COH and R–C≡CSH compounds
Entity
UAM. Departamento de QuímicaPublisher
SpringerDate
2023-03-03Citation
10.1007/s00214-023-02967-0
Theoretical Chemistry Accounts 142.28 (2023): 1-10
ISSN
1432-881X (print); 1432-2234 (online)DOI
10.1007/s00214-023-02967-0Funded by
This work was carried out with fnancial support from the projects PID2021-125207NB-C31, PID2021-125207NB-C32 and PID2019-110091GB-I00 of the Ministerio de Ciencia, Innovación y Universidades of Spain (MICINN). Finally, the authors thank the Centro de Computación Científca of the UAM (CCC-UAM) for the generous allocation of computer time and continued technical support. J.-C.G. thanks the CNES for a grant (50006558)Project
Gobierno de España. PID2021-125207NB-C31; Gobierno de España. PID2021-125207NB-C32Editor's Version
https://doi.org/10.1007/s00214-023-02967-0Subjects
G4 calculations; Intrinsic acidity; Intrinsic basicity; Ynethiols (R-C≡CSH); Ynols (R-C≡COH); QuímicaRights
© The Author(s) 2023Abstract
The effect of changing the nature of the R substituent from the first row (H, Li, BeH, BH2, CH3, NH2, OH and F) to second row (Na, MgH, AlH2, SiH3, PH2, SH and Cl) on the intrinsic acidity and basicity of R–C≡COH and R–C≡CSH compounds was investigated through the use of G4 high-level ab initio calculation. The variation of the acidity and basicity of the R–C≡CSH derivatives as a function of R is practically parallel to that found for the corresponding R–C≡COH analogs; though the basicities of the former are 9–14% higher than those of the latter, the acidity gap being very small (~ 2%). When this analysis is extended to the derivatives in which the triple CC bond is replaced by a double or single bond, it is found that the acidity gap increases systematically as the CC bond goes from triple to single; whereas, as expected for the basicity, the trend is the opposite. Quite surprisingly, however, the variation of the basicity of R–C≡CX (X = OH, SH) compounds with the nature of the first-row substituents, R, is remarkably different from that produced by the second-row analogs. The same is observed as far as intrinsic acidities are concerned. These dissimilarities reflect the rather different changes in the strength of the CC and the CX (X = OH, SH) bonds when a first-row substituent is replaced by the second-row analog, as reflected in the atoms in molecules (AIM), natural bond orbital (NBO) and the electron localization function (ELF) analyses of the corresponding species
Files in this item
Google Scholar:Mo Romero, Otilia
-
Alkorta, Ibon
-
Guillemin, Jean Claude
-
Yáñez Montero, Manuel
This item appears in the following Collection(s)
Related items
Showing items related by title, author, creator and subject.