Solvent effects on oxygen-17 chemical shifts in methyl formate: Linear solvation shift relationships
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 17O chemical shifts of methyl formate (MF). The influence of the solvents upon the carbonyl oxygen chemical shifts is smaller for MF than...
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todo:paper_10907807_v148_n1_p1_DeKowalewski2023-10-03T16:04:57Z Solvent effects on oxygen-17 chemical shifts in methyl formate: Linear solvation shift relationships De Kowalewski, D.G. Kowalewski, V.J. Contreras, R.H. Díez, E. Casanueva, J. San Fabián, J. Esteban, A.L. Galache, M.P. article 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 17O chemical shifts of methyl formate (MF). The influence of the solvents upon the carbonyl oxygen chemical shifts is smaller for MF than for N-methylform-amide (NMF). The influence (in parts per million) of the solvent polarity-polarizability reduces from −21.9π* in amides to −9.6π* in MF. The influence of the solvent hydrogen-bond-donor acidities reduces from −42.0α in formamides to −16.9α in MF. The solvent effects upon the dicoordinated oxygen chemical shifts of MF are smaller in magnitude and opposite in direction, i.e., 4.8π* and 2.6α, than those for the carbonyl oxygen. 17O hydration shifts have been calculated for the NMF + (H2O)6 and MF + (H2O)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. © 2001 Academic Press. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_10907807_v148_n1_p1_DeKowalewski |
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Universidad de Buenos Aires |
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I-28 |
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
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article |
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article De Kowalewski, D.G. Kowalewski, V.J. Contreras, R.H. Díez, E. Casanueva, J. San Fabián, J. Esteban, A.L. Galache, M.P. Solvent effects on oxygen-17 chemical shifts in methyl formate: Linear solvation shift relationships |
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article |
| description |
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 17O chemical shifts of methyl formate (MF). The influence of the solvents upon the carbonyl oxygen chemical shifts is smaller for MF than for N-methylform-amide (NMF). The influence (in parts per million) of the solvent polarity-polarizability reduces from −21.9π* in amides to −9.6π* in MF. The influence of the solvent hydrogen-bond-donor acidities reduces from −42.0α in formamides to −16.9α in MF. The solvent effects upon the dicoordinated oxygen chemical shifts of MF are smaller in magnitude and opposite in direction, i.e., 4.8π* and 2.6α, than those for the carbonyl oxygen. 17O hydration shifts have been calculated for the NMF + (H2O)6 and MF + (H2O)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. © 2001 Academic Press. |
| format |
JOUR |
| author |
De Kowalewski, D.G. Kowalewski, V.J. Contreras, R.H. Díez, E. Casanueva, J. San Fabián, J. Esteban, A.L. Galache, M.P. |
| author_facet |
De Kowalewski, D.G. Kowalewski, V.J. Contreras, R.H. Díez, E. Casanueva, J. San Fabián, J. Esteban, A.L. Galache, M.P. |
| author_sort |
De Kowalewski, D.G. |
| title |
Solvent effects on oxygen-17 chemical shifts in methyl formate: Linear solvation shift relationships |
| title_short |
Solvent effects on oxygen-17 chemical shifts in methyl formate: Linear solvation shift relationships |
| title_full |
Solvent effects on oxygen-17 chemical shifts in methyl formate: Linear solvation shift relationships |
| title_fullStr |
Solvent effects on oxygen-17 chemical shifts in methyl formate: Linear solvation shift relationships |
| title_full_unstemmed |
Solvent effects on oxygen-17 chemical shifts in methyl formate: Linear solvation shift relationships |
| title_sort |
solvent effects on oxygen-17 chemical shifts in methyl formate: linear solvation shift relationships |
| url |
http://hdl.handle.net/20.500.12110/paper_10907807_v148_n1_p1_DeKowalewski |
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