| Texto completo | |
| Autor(es): |
Neto, Alvaro Cunha
[1]
;
dos Santos, Francisco P.
[1]
;
Contreras, Ruben H.
[2, 3]
;
Rittner, Roberto
[1]
;
Tormena, Claudio F.
[1]
Número total de Autores: 5
|
| Afiliação do(s) autor(es): | [1] Univ Estadual Campinas, Inst Chem, Dept Organ Chem, BR-13084971 Sao Paulo - Brazil
[2] Consejo Nacl Invest Cient & Tecn, Buenos Aires, DF - Argentina
[3] Univ Buenos Aires, Fac Ciencias Exactas & Nat, Dept Phys, Buenos Aires, DF - Argentina
Número total de Afiliações: 3
|
| Tipo de documento: | Artigo Científico |
| Fonte: | Journal of Physical Chemistry A; v. 112, n. 46, p. 11956-11959, NOV 20 2008. |
| Citações Web of Science: | 13 |
| Resumo | |
A conceptual analysis of the CLOPPA (Contributions from Localized Orbitals within the Polarization Propagator Approach) expressions that deconvolute NMR spin-spin coupling constants {[}Diz A. C.; Giribet C. G.; Ruiz de Azua, M. C.; Contreras, R. H. Int. J. Quantum Chem. 1990, 37, 663.] into orbital contributions can provide an in-depth insight into the features of the electronic molecular structure that originate a given (1)J(CH) experimental trend. In this work, several 1-X-cyclopropane derivatives are taken as model compounds to apply such ideas to rationalize substituent effects on the Fermi contact term Of (1)J(CLH) spin-spin coupling. It is shown that in this type of coupling, its experimental trend, as measured in this work, cannot be accounted for with only the ``bond{''} and the ``other bond{''} contributions, requiring the inclusion of ``other antibonding contributions{''}. Such effect is discussed in terms of hyperconjugative interactions. (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 |