title: Solvent effects on oxygen-17 chemical shifts in methyl formate: linear solvation shift relationships.
abstract: A multiple linear regression analysis has been carried out using the Kamlet-Abboud-Taft solvatochromic parameters in order to quantify the solvent effects on the (17)O chemical shifts of methyl formate (MF). The influence of the solvents upon the carbonyl oxygen chemical shifts is smaller for MF than for N-methylformamide (NMF). The influence (in parts per million) of the solvent polarity-polarizability reduces from -21.9pi* in amides to -9.6pi* in MF. The influence of the solvent hydrogen-bond-donor acidities reduces from -42.0alpha in formamides to -16.9alpha in MF. The solvent effects upon the dicoordinated oxygen chemical shifts of MF are smaller in magnitude and opposite in direction, i.e., 4.8pi* and 2.6alpha, than those for the carbonyl oxygen. (17)O hydration shifts have been calculated for the NMF + (H(2)O)(6) and MF + (H(2)O)(5) complexes by the ab initio GIAO method at the 6-311 + G** level. The hydration shifts calculated for the carbonyl oxygens of NMF and MF and for the dicoordinated oxygen of MF, -102.4, -64.7, and 17.6 ppm, respectively, show the same trend as the corresponding empirical hydration shifts, -101.7, -42.0, and 14.2 ppm.
authors.affiliation: Departamento de Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires and CONICET (LANAIS RMN-500), Pabellón I, Ciudad Universitaria, Buenos Aires, 1428, Argentina.
authors.lastname: de Kowalewski DG
authors.forename: V J
authors.initials: VJ
authors.lastname: Kowalewski
authors.forename: R H
authors.initials: RH
authors.lastname: Contreras
authors.forename: E
authors.initials: E
authors.lastname: Díez
authors.forename: J
authors.initials: J
authors.lastname: Casanueva
authors.lastname: San Fabián J
authors.forename: A L
authors.initials: AL
authors.lastname: Esteban
authors.forename: M P
authors.initials: MP
authors.lastname: Galache