| Texto completo | |
| Autor(es): |
Contreras, Ruben H.
[1]
;
Provasi, Patricio F.
[2, 3, 4]
;
dos Santos, Francisco P.
[5]
;
Tormena, Claudio F.
[5]
Número total de Autores: 4
|
| Afiliação do(s) autor(es): | [1] Univ Buenos Aires, FCEyN, Dept Phys, Buenos Aires, DF - Argentina
[2] Consejo Nacl Invest Cient & Tecn, RA-1033 Buenos Aires, DF - Argentina
[3] Northeastern Univ, FACENA, Dept Phys, Corrientes - Argentina
[4] Consejo Nacl Invest Cient & Tecn, Corrientes - Argentina
[5] Univ Estadual Campinas, Dept Organ Chem, Inst Chem, BR-13084971 Sao Paulo - Brazil
Número total de Afiliações: 5
|
| Tipo de documento: | Artigo Científico |
| Fonte: | Magnetic Resonance in Chemistry; v. 47, n. 2, p. 113-120, FEB 2009. |
| Citações Web of Science: | 13 |
| Resumo | |
In this work it was sought to explore the versatility of germinal spin-spin coupling constants, (2)J(XY) SSCCs, as probes for stereochemical studies. A set of compounds, where their experimental (2)J(XY) SSCCs through the X-C-Y molecular fragment are predicted to be sensitive to hyperconjugative interactions involving either bonding or antibonding orbitals containing the C carbon atom ('coupling pathway'), were analyzed. SSCC calculations were performed for some selected examples using the second order polarization propagator approximation (SOPPA) method or within the DFT-B3LYP framework. Hyperconjugative interactions were calculated within the Natural Bond Orbital (NBO) approach. Results are condensed in two qualitative rules: Rule I(M) - hyperconjugative interactions transferring charge into the coupling pathway yield a positive increase to the Fermi contact (FC), contribution to (2)K(XY) reduced spin-spin coupling constants (RSSCC), and Rule II(M) - hyperconjugative interactions transferring charge from the coupling pathway yield a negative increase to the FC contribution to (2)K(XY) RSSCC. Copyright (C) 2008 John Wiley \& Sons, Ltd. (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: | 06/03980-2 - Interacoes de orbitais e seus efeitos nas constantes de acoplamento escalar em rmn: estudo experimental e teorico. |
| Beneficiário: | Claudio Francisco Tormena |
| Modalidade de apoio: | Auxílio à Pesquisa - Regular |