| Texto completo | |
| Autor(es): |
Piscelli, Bruno A.
;
Buhl, Michael
;
Cormanich, Rodrigo A.
;
O'hagan, David
Número total de Autores: 4
|
| Tipo de documento: | Artigo Científico |
| Fonte: | ANGEWANDTE CHEMIE-INTERNATIONAL EDITION; v. N/A, p. 15-pg., 2025-11-11. |
| Resumo | |
The RCH2F and RCHF2 groups are substituents of interest in medicinal and agrochemicals products. They have a polar aspect relative to the methyl (RCH3) or trifluoromethyl (RCF3) groups which results in a lowering of Log P's (water affinity). Here we use a computational approach to explore the nature of the interaction between RCH2F and RCHF2 in methanes and ethanes with chloride ion (and water), as a hydrogen bonding acceptor. A key observation is that the hydrogen atoms geminal to the fluorine(s) become less positively charged with increasing fluorination, a trend anticipated to weaken, not strengthen, their hydrogen bonding interactions. However this study demonstrates a dominating role for the electrostatic interaction of the acceptor with the CF carbons and profiles a shift in negative charge density from hydrogen to the carbon and fluorine(s) as chloride ion (or water) approach. The common occurrence of blue shifts (shortening C & horbar;H length) in these 'improper' or 'non-classical' hydrogen bonds is also explored and is correlated with the electrostatic interactions between the acceptor and the carbon atoms. These observations are extended to C3 & horbar;C6 alicyclic rings containing these motifs and predict particularly strong interactions energies between chloride ion and specifically designed organo-fluoro alicycles. (AU) | |
| Processo FAPESP: | 18/03910-1 - Estudos físico-químicos de compostos orgânicos fluorados: abordagens experimental e teórica |
| Beneficiário: | Rodrigo Antonio Cormanich |
| Modalidade de apoio: | Auxílio à Pesquisa - Jovens Pesquisadores |
| Processo FAPESP: | 23/14064-2 - Modelagem da interação de ciclohexanos Janus-face com dsDNA e ssDNA. |
| Beneficiário: | Bruno de Almeida Piscelli |
| Modalidade de apoio: | Bolsas no Exterior - Estágio de Pesquisa - Doutorado Direto |
| Processo FAPESP: | 22/10156-7 - Estudo experimental e teórico dos efeitos estereoeletrônicos e arranjo supramolecular de compostos organofluorados |
| Beneficiário: | Bruno de Almeida Piscelli |
| Modalidade de apoio: | Bolsas no Brasil - Doutorado Direto |