Abstract: The known solvent dependence of 1J(Cc,Hf) and 2J(C1,Hf) couplings in acetaldehyde is studied from a theoretical viewpoint based on the density functional theory approach where the dielectric solvent effect is taken into account with the polarizable continuum model. The four terms of scalar couplings, Fermi contact, paramagnetic spin orbital, diamagnetic spin orbital and spin dipolar, are calculated but the solvent effect analysis is restricted to the first term since for both couplings it is by far the dominant contribution. Experimental trends of Δ1J(Cc,Hf) and Δ2J(C1,Hf) Vs ε (the solvent dielectric constant) are correctly reproduced although they are somewhat underestimated. Specific interactions between solute and solvent molecules are studied for dimethylsulfoxide, DMSO, solutions considering two different one-to-one molecular complexes between acetaldehyde and DMSO. They are determined by interactions of type C=O---H---C and S=O---H---C, and the effects of such interactions on 1J(Cc,Hf) and 2J(C1,Hf) couplings are analyzed. Even though only in a semiquantitative way, it is shown that the effect of such interactions on the solvent effects, of Δ1J(Cc,Hf) and Δ2J(C1,Hf), tend to improve the agreement between calculated and experimental values. These results seem to indicate that a continuum dielectric model has not enough flexibility for describing quantitatively solvent effects on spin-spin couplings. Apparently, even for relatively weak hydrogen bonding, the contribution from “direct” interactions is of the same order of magnitude as the “dielectric” effect.
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Zaccari, D.; Barone, V.; Peralta, J.E.; Contreras, R.H.; Taurian, O.E.; Díez, E.; Esteban, A. Solvent Effects on Nuclear Magnetic Resonance 2J(C,Hf) and 1J(C,Hf) Spin–Spin Coupling Constants in Acetaldehyde. Int. J. Mol. Sci. 2003, 4, 93-106.
Zaccari D, Barone V, Peralta JE, Contreras RH, Taurian OE, Díez E, Esteban A. Solvent Effects on Nuclear Magnetic Resonance 2J(C,Hf) and 1J(C,Hf) Spin–Spin Coupling Constants in Acetaldehyde. International Journal of Molecular Sciences. 2003; 4(3):93-106.
Zaccari, Daniel; Barone, Verónica; Peralta, Juan E.; Contreras, Rubén H.; Taurian, Oscar E.; Díez, Ernesto; Esteban, Angel. 2003. "Solvent Effects on Nuclear Magnetic Resonance 2J(C,Hf) and 1J(C,Hf) Spin–Spin Coupling Constants in Acetaldehyde." Int. J. Mol. Sci. 4, no. 3: 93-106.