1 J CH Coupling in Benzaldehyde Derivatives: Ortho Substitution Effect

Angelita Nepel; Renan V Viesser; Cláudio F Tormena

doi:10.1021/acsomega.8b03035

¹ J _CH Coupling in Benzaldehyde Derivatives: Ortho Substitution Effect

ACS Omega. 2019 Jan 17;4(1):1494-1503. doi: 10.1021/acsomega.8b03035. eCollection 2019 Jan 31.

Authors

Angelita Nepel¹, Renan V Viesser¹, Cláudio F Tormena¹

Affiliation

¹ Institute of Chemistry, University of Campinas-UNICAMP, P.O. Box 6154, 13083-970 Campinas, SP, Brazil.

Abstract

The natural J-coupling (NJC) method is applied to analyze the Fermi contact contribution of the NMR spin-spin coupling constant decomposing this contribution in terms of natural localized molecular orbitals. We investigated the influence of the basis set on the NJC analysis for the formyl group coupling constant (¹ J _CHf) of benzaldehyde derivatives. NJC and other NBO analyses, like steric and natural Coulombic energy, were chosen to explain the influence of electron-donating and electron-withdrawing groups on ¹ J _CHf for some substituted benzaldehydes (Me, OH, OMe, F, Cl, Br, I, and NO₂). For the ortho derivatives, electronegative substituents near the C-Hf bond increase the ¹ J _CHf coupling. This effect could be related to an increase in formyl carbon s character and changes in the carbon and hydrogen natural charges. This indicates that the substituents in ortho have a proximity effect on ¹ J _CHf coupling mainly of electrostatic origin instead of the expected hyperconjugative interactions.