Charge density analysis of some processes involving intramolecular hydrogen transfer |
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Authors: | Marcos Mandado Ana M Graña |
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Institution: | a Departamento de Química Física, Facultade de Química, Universidade de Vigo, Lagoas-Marcosende s/n, 36200 Vigo, Galicia, Spain b Department of Chemistry, University of Antwerp (UA), Universiteitplein 1, B-2610 Antwerpen, Belgium |
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Abstract: | The variations in topology of the electron density along the reaction paths of the keto-enol tautomerism of acetaldehyde, the pinacol rearrangement of protonated 1,2-ethanediol, and the unimolecular decomposition of methanediol, were studied as examples of hydrogen transfer between, respectively, C?O, C?C, and O?O atoms. The evolution of atomic charges, determined using two different atomic partitionings (AIM and Hirshfeld), indicates that the main electronic charge transfer in keto-enol tautomerism takes place between the migrating hydrogen and the carbon of the carbonyl group. The topology of the electron density demonstrates that a hydrogen-bridge structure is never formed along the reaction path of the pinacol rearrangement. The methanediol decomposition follows a concerted mechanism with very small variations in the atomic charges. |
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Keywords: | Keto-enol tautomerism Pinacol rearrangement Methanediol decomposition AIM theory Hirshfeld partitioning |
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