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dc.creatorSilva, Daniela Rodrigues-
dc.creatorSantos, Lucas de Azevedo-
dc.creatorHamlin, Trevor A.-
dc.creatorBickelhaupt, F. Matthias-
dc.creatorFreitas, Matheus P.-
dc.creatorGuerra, Célia Fonseca-
dc.identifier.citationSILVA, D. R. et al. Dipolar repulsion in α-halocarbonyl compounds revisited. Physical Chemistry Chemical Physics, [S.l.], v. 23, p. 20883-20891, Sept. 2021. DOI: 10.1039/d1cp02502c.pt_BR
dc.description.abstractThe 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.pt_BR
dc.publisherRoyal Society of Chemistrypt_BR
dc.rightsacesso abertopt_BR
dc.sourcePhysical Chemistry Chemical Physicspt_BR
dc.subjectRotational energy profilespt_BR
dc.subjectOrbital interactionspt_BR
dc.subjectElectrostatic interactionspt_BR
dc.titleDipolar repulsion in α-halocarbonyl compounds revisitedpt_BR
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