Resumen
Methyl nitrite has a normal 2.09 kcal/mol methyl rotation barrier in the Z-conformer, but only a small 0.03-0.06 kcal/mol barrier in the E-conformer as determined from microwave spectra (Turner et al., J. Phys. Chem., 83 (1979) 1473). Using dependable calculational methods, we show that this is a general result which carries over to another E-methyl ester, E-methyl formate, which does not have a sterically large substituent on the acid group, and is not specific to methyl nitrite alone. The small methyl barriers in E-methyl nitrite and E-methyl formate result from the absence of large steric interactions. Replacing H in the formyl group by sterically larger F, results in a normal O-methyl torsional barrier calculated to be 1.8 kcal/mol in the E-methyl fluoroformate.
Idioma original | Inglés |
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Páginas (desde-hasta) | 239-248 |
Número de páginas | 10 |
Publicación | Journal of Molecular Structure |
Volumen | 485-486 |
DOI | |
Estado | Publicada - 10 ago. 1999 |
Publicado de forma externa | Sí |