Dipolar repulsion in α-halocarbonyl compounds revisited.

ABSTRACT: The concept of dipolar repulsion has been widely used to explain several phenomena in organic chemistry, including the conformational preferences of carbonyl compounds. This model, in which atoms and bonds are viewed as point charges and dipole moment vectors, respectively, is however oversimplified. To provide a causal model rooted in quantitative molecular orbital theory, we have analyzed the rotational isomerism of haloacetaldehydes OHC-CH₂X (X = F, Cl, Br, I), using relativistic density functional theory. We have found that the overall trend in the rotational energy profiles is set by the combined effects of Pauli repulsion (introducing a barrier around gauche that separates minima at syn and anti), orbital interactions (which can pull the anti mi

SUBMITTER: Rodrigues Silva D 

PROVIDER: S-EPMC8479779 | biostudies-literature | 2021 Sep

REPOSITORIES: biostudies-literature