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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Publicado: 2001
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Acceso en línea:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_10907807_v148_n1_p1_DeKowalewski
http://hdl.handle.net/20.500.12110/paper_10907807_v148_n1_p1_DeKowalewski
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
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spelling paper:paper_10907807_v148_n1_p1_DeKowalewski2023-06-08T16:06:41Z Solvent effects on oxygen-17 chemical shifts in methyl formate: Linear solvation shift relationships 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. 2001 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_10907807_v148_n1_p1_DeKowalewski http://hdl.handle.net/20.500.12110/paper_10907807_v148_n1_p1_DeKowalewski
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic article
spellingShingle article
Solvent effects on oxygen-17 chemical shifts in methyl formate: Linear solvation shift relationships
topic_facet 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.
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
publishDate 2001
url https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_10907807_v148_n1_p1_DeKowalewski
http://hdl.handle.net/20.500.12110/paper_10907807_v148_n1_p1_DeKowalewski
_version_ 1768546598175899648

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