| Texto completo | |
| Autor(es): |
Oliveira, Vytor Pinheiro
[1]
;
Marcial, Bruna Luana
[2]
;
Machado, Francisco B. C.
[1]
;
Kraka, Elfi
[3]
Número total de Autores: 4
|
| Afiliação do(s) autor(es): | [1] Inst Tecnol Aeronaut ITA, Dept Quim, BR-12228900 Sao Jose Dos Campos, SP - Brazil
[2] Inst Fed Goiano IF Goiano, Nucleo Quim, Campus Morrinhos, Morrinhos, Go - Brazil
[3] Southern Methodist Univ, Dept Chem, Computat & Theoret Chem Grp CATCO, 3215 Daniel Ave, Dallas, TX 75275 - USA
Número total de Afiliações: 3
|
| Tipo de documento: | Artigo Científico |
| Fonte: | CHEMPLUSCHEM; v. 86, n. 8, p. 1199-1210, AUG 2021. |
| Citações Web of Science: | 1 |
| Resumo | |
The bond strength and nature of a set of 32 Togni-like reagents have been investigated at the M062X/def2-TZVP(D) level of theory in acetonitrile described with the SMD continuum solvent model, to rationalize the main factors responsible for their thermodynamic stability in different conformations, and trifluoromethylation capabilities. For the assessment of bond strength, we utilized local stretching force constants and associated bond strength orders, complemented with local features of the electron density to access the nature of the bonds. Bond dissociation energies varied from 31.6 to 79.9 kcal/mol depending on the polarizing power of the ligand trans to CF3. Based on the analysis of the Laplacian of the density, we propose that the charge-shift bond character plays an important role in the stability of the molecules studied, especially for those containing I-O bonds. New insights on the trans influence and on possible ways to fine-tune the stability of these reagents are provided. (AU) | |
| Processo FAPESP: | 19/25105-6 - Hidrocarbonetos aromáticos policíclicos (PAH's): dopagem, vacância, reatividade, estados excitados: uma abordagem multiconfiguracional |
| Beneficiário: | Francisco Bolivar Correto Machado |
| Modalidade de apoio: | Auxílio à Pesquisa - Regular |
| Processo FAPESP: | 18/13673-7 - Desenho de novos reagentes de iodo hipervalente com base em estudos teóricos de elevada acurácia |
| Beneficiário: | Vytor Pinheiro Oliveira |
| Modalidade de apoio: | Bolsas no Brasil - Pós-Doutorado |