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(Reference retrieved automatically from Web of Science through information on FAPESP grant and its corresponding number as mentioned in the publication by the authors.)

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

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Author(s):
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]
Total Authors: 7
Affiliation:
[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
Total Affiliations: 4
Document type: Journal article
Source: Journal of Physical Chemistry A; v. 113, n. 36, p. 9874-9880, SEP 10 2009.
Web of Science Citations: 8
Abstract

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)

FAPESP's process: 08/06282-0 - Transmission mechanism of scalar spin-spin coupling constants involving fluorine atom.
Grantee:Roberto Rittner Neto
Support Opportunities: Regular Research Grants