Qualitative Study of Substituent Effects on NMR N-15 and O-17 Chemical Shifts

Autor(es)

Contreras, Ruben H. ^{[1, 2]} ; Llorente, Tomas ^{[1, 2]} ; Pagola, Gabriel I. ^{[1, 2]} ; Bustamante, Manuel G. ^{[1, 2]} ; Pasqualini, Enrique E. ^[3] ; Melo, Juan I. ^{[1, 2]} ; Tormena, Claudio F. ^[4]

Afiliação do(s) autor(es)

^[1] Consejo Nacl Invest Cient & Tecn, RA-1033 Buenos Aires, DF - Argentina

^[2] Univ Buenos Aires, FCE&N, Dept Phys, Buenos Aires, DF - Argentina

^[3] Argentine Natl Atom Energy Commiss, Buenos Aires, DF - Argentina

^[4] Univ Estadual Campinas, Inst Chem, Dept Organ Chem, BR-13084971 Sao Paulo - Brazil

• Tipo de documento: Artigo Científico
• Fonte: Journal of Physical Chemistry A; v. 113, n. 36, p. 9874-9880, SEP 10 2009.
• Citações Web of Science: 8

Resumo

A qualitative approach to analyze the electronic origin of substituent effects on the paramagnetic part of chemical shifts is described and applied to few model systems, where its potentiality can be appreciated. The formulation of this approach is based on the following grounds. The influence of different inter- or intramolecular interactions on a second-order property can be qualitatively predicted if it can be 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 that define some experimental trends of magnetic shielding constants. This approach is applied first to study the electronic origin of methyl-beta substituent effects on both (15)N and (17)O chemical shifts, and afterward it is applied to a couple of examples of long-range substituent effects originated in charge transfer interactions such as the conjugative effect in aromatic compounds and sigma-hyperconjugative interactions in saturated multicyclic compounds. (AU)

• Processo FAPESP: 08/06282-0 - Estudo do mecanismo de transmissão de constantes de acoplamento escalar envolvendo o átomo de flúor
• Beneficiário: Roberto Rittner Neto
• Modalidade de apoio: Auxílio à Pesquisa - Regular
• 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