Dipolar repulsion in α-halocarbonyl compounds revisited

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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 minimum towards anticlinal to maximize hyperconjugation), and electrostatic interactions. Only for X = F, not for X = Cl-I, electrostatic interactions push the preference from syn to anti. Our bonding analyses show how this trend is related to the compact nature of F versus the more diffuse nature of the heavier halogens.

Original languageEnglish
Pages (from-to)20883-20891
Number of pages9
JournalPhysical Chemistry Chemical Physics
Issue number37
Early online date1 Sept 2021
Publication statusPublished - 7 Oct 2021

Bibliographical note

Funding Information:
The authors are grateful to the Netherlands Organization for Scientific Research (NWO), the Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq), the Coorde-nação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES), and the Fundação de Amparo à Pesquisa do Estado de Minas Gerais (FAPEMIG) for financial support.

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