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Importance of Electronic Delocalization on the C−N Bond Rotation in HCX(NH2) (X = O, NH, CH2, S, and Se)
journal contribution
posted on 2003-11-20, 00:00 authored by Yirong Mo, Paul von Ragué Schleyer, Wei Wu, Menghai Lin, Qianer Zhang, Jiali GaoA block-localized wave function method, which in effect can switch off conventional conjugation and
hyperconjugation effects, is employed to investigate the origin of the rotational barriers in formamide and its
analogues. It is found that the resonance between the π electrons on the CX double bond and the nitrogen
lone pair significantly stabilizes the planar conformation in HCXNH2 (X = O, NH, CH2, S, and Se). The
absolute resonance energy follows the order of formamide < thioformamide < selenoformamide, with predicted
vertical resonance energies of −25.5, −35.7, and −37.6 kcal/mol, respectively. The computed vertical resonance
energies for X = O, NH, and CH2 are −25.5, −22.5, and −19.1 kcal/mol, respectively, which follow the
decreasing trend of electronegativity. Although the rotational barrier about the C−N bond in vinylamine (4.5
kcal/mol) is much smaller than that of formamide (15.7 kcal/mol), the resonance energy in vinylamine is of
the same order as that of formamide (−19.1 versus −25.5 kcal/mol). Consequently, the rotational barrier in
formamide cannot be simply regarded as a result of the carbonyl polarization as proposed in early studies. In
fact, energy decomposition results reveal that resonance and σ-framework steric effects are equally important
for the estimated difference in rotational barrier. Ab initio valence bond calculations are performed to investigate
the electronic delocalization in formamide and its analogues. Examination of the electron density difference
between the adiabatic (delocalized) and diabatic (localized) states revealed that the resonance in the planar
formamide shifts electron density from nitrogen both to carbon and to oxygen, supporting the conventional
resonance model. This is accompanied by the opposing migration of the σ charge density, making the integrated
atomic charges smaller than that expected from pure π delocalization.