Ab initio studies of structural features not easily amenable to experiment: Part 20. Structural aspects of ethyl groups

Abstract

The molecular structures of a number of stable conformations of ethanol, ethylamine, methylethyl ether, methylethylamine and of the ethyl anion have been determined by ab initio geometry optimizations using Pulay's Force method on the 4–21G level. The calculated geometries characterize the extent to which structural groups in a molecule are sensitive to asymmetries in their environment. Characteristic structural trends are consistently found for the CH bond distances and CCH angles in the C 2H 5 groups of trans-ethanol, trans-methylethyl ether and in the ethyl anion. They differ from those previously found for C 2H 5 groups in hydrocarbons. There is qualitative disagreement between the trends calculated for CH bond distances in trans-ethanol and trans-methylethyl ether and those found in the microwave substitution structures of these compounds. Since the substitution parameters are unresolved because of relatively large experimental or model uncertainties, it is presently impossible to decide whether this discrepancy is the result of computational or experimental deficiency. The methyl groups in methylethyl ether and methylethylamine exhibit the characteristic structural distortions which are usually found for CH 3 groups adjacent to electron lone pairs. The CC bond distances in C 2H 5 in the systems studied here are sensitive to the conformational arrangement of ethyl relative to the rest of a system in a way which can be rationalized by orbital interactions involving antibonding orbitals on sp 3-hybridized carbon atoms. The calculated conformational stabilities agree qualitatively with experimental trends, except in the case of ethanol where the trans — gauche energy difference is small (about 0.1 kcal mol −1) and within the uncertainties of the calculations. Our conformational energies for CH 3CH 2NH 2 are in disagreement with a previous ab initio investigation based on a comparison of unoptimized standard geometries. In general, the agreement between calculated structural parameters and corresponding reliable experimental values is very good in all comparable cases.