Artículos de revistas
Analysis of the electronic origin of the1JCH spin-spin coupling trend in 1-X-cyclopropanes: Experimental and DFT study
Fecha
2008-11Registro en:
Neto, Álvaro Cunha; Dos Santos, Francisco P.; Contreras, Ruben Horacio; Rittner, Roberto; Tormena, Cláudio F.; Analysis of the electronic origin of the1JCH spin-spin coupling trend in 1-X-cyclopropanes: Experimental and DFT study; American Chemical Society; Journal of Physical Chemistry A; 112; 46; 11-2008; 11956-11959
1089-5639
CONICET Digital
CONICET
Autor
Neto, Álvaro Cunha
Dos Santos, Francisco P.
Contreras, Ruben Horacio
Rittner, Roberto
Tormena, Cláudio F.
Resumen
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 Azúa, 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 1JCH 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 1JC1,H 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. © 2008 American Chemical Society.