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Conformation energy around the N( sp 3 )O single bond
Author(s) -
Tronchet Jean M. J.,
Komaromi Istvan
Publication year - 1994
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.540151005
Subject(s) - chemistry , bond , single bond , computational chemistry , bond energy , crystallography , molecule , organic chemistry , business , alkyl , finance
A detailed conformational analysis was performed on simple substituted hydroxylamines using either ab initio (from HF/6‐31G* to RQCISD/6‐311G**) or popular semiempirical (MNDO, AM1, PM3) methods to ascertain the allowed conformations and to establish the influence of the level of theory on the results. All the ab initio results (provision being made for their expected divergences) are similar and show a simple twofold character for the > NO rotational energy, without any appreciable populations of the cis conformer. On the other hand, the predictive value of the semiempirical methods for structural and energetical parameters of molecules bearing > NO moieties is limited, a situation like that prevailing for peptide bonds. The inversional barriers for the methyl‐substituted hydroxylamines were also calculated and compared to the corresponding rotational energy barriers. Rotation is generally favored over inversion for hydroxylamine and its methylated derivatives. © 1994 by John Wiley & Sons, Inc.