| Texto completo | |
| Autor(es): |
Vilcachagua, Janaina Dantas
[1]
;
Ducati, Lucas C.
[1]
;
Rittner, Roberto
[1]
;
Contreras, Ruben H.
[2, 3]
;
Tormena, Claudio F.
[1]
Número total de Autores: 5
|
| Afiliação do(s) autor(es): | [1] Univ Estadual Campinas, Inst Chem, BR-13084971 Campinas, SP - Brazil
[2] Univ Buenos Aires, FCEyN, Dept Phys, Buenos Aires, DF - Argentina
[3] IFIBA CONICET, Buenos Aires, DF - Argentina
Número total de Afiliações: 3
|
| Tipo de documento: | Artigo Científico |
| Fonte: | Journal of Physical Chemistry A; v. 115, n. 7, p. 1272-1279, FEB 24 2011. |
| Citações Web of Science: | 26 |
| Resumo | |
Interesting insight into the electronic molecular structure changes associated with substituent effects on the Fermi contact (FC) and paramagnetic spin-orbit (PSO) terms of (1)J(CF) NMR coupling constants (SSCCs) in o-X-, m-X-, and p-X-fluorobenzenes (X = NH(2); NO(2)) is presented. The formulation of this approach is based on the influence of different conjugative and hyperconjugative interactions on a second-order property, which can be qualitatively predicted if it is known how they affect the main virtual excitations entering into that second-order property. A set of consistent approximations are introduced in order to analyze the behavior of occupied and virtual orbitals, which define some experimental trends for (1)J(CF) spin-spin coupling constants. In addition, DFT hybrid functionals were used, and a similar degree of confidence to compute the (1)J(CF) with those observed for the SOPPA(CCSD) method was obtained. The (1)J(CF) SSCCs for ezetimibe, a commercially fluorinated drug used to reduce cholesterol levels, were measured and DFT-calculated, and the qualitative approach quoted above was applied. As a byproduct, a possible method to determine experimentally a significant PSO contribution to (1)J(CF) SSCCs is discussed. (AU) | |
| Processo FAPESP: | 05/59649-0 - Estudos de estrutura eletrônica e molecular através de métodos espectroscópicos e cálculos teóricos |
| Beneficiário: | Roberto Rittner Neto |
| Modalidade de apoio: | Auxílio à Pesquisa - Temático |
| Processo FAPESP: | 06/02783-9 - Desenvolvimento de funções de base para cálculo teórico de acoplamentos J(P,P), J(P,C) e J(P,H) |
| Beneficiário: | Lucas Colucci Ducati |
| Modalidade de apoio: | Bolsas no Brasil - Doutorado |