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Solvent Effects on Oxygen-17 Chemical Shifts in Methyl Formate: Linear Solvation Shift Relationships

✍ Scribed by Dora G. de Kowalewski; Valdemar J. Kowalewski; Ruben H. Contreras; Ernesto Dı́ez; Jorge Casanueva; Jesús San Fabián; Angel L. Esteban; Maria P. Galache

Publisher
Elsevier Science
Year
2001
Tongue
English
Weight
100 KB
Volume
148
Category
Article
ISSN
1090-7807

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✦ Synopsis

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.

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