AI Article Synopsis
- The concept of dipolar repulsion has been a common explanation in organic chemistry for the behavior of carbonyl compounds, but it's overly simplistic.
- We analyzed haloacetaldehydes using advanced molecular orbital theory to uncover how different factors influence their rotational isomerism.
- Findings indicate that Pauli repulsion, orbital interactions, and electrostatic interactions collectively shape energy profiles, with specific effects based on the size and nature of the halogens involved.
Article 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-CHX (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 that separates minima at and ), orbital interactions (which can pull the minimum towards to maximize hyperconjugation), and electrostatic interactions. Only for X = F, not for X = Cl-I, electrostatic interactions push the preference from to . Our bonding analyses show how this trend is related to the compact nature of F the more diffuse nature of the heavier halogens.
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| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC8479779 | PMC |
| http://dx.doi.org/10.1039/d1cp02502c | DOI Listing |
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