Looking inside: Analysis of keto‐enol equilibrium using agent‐based models

• Published in: Journal of physical organic chemistry 2024-03, Vol.37 (3)
• Main Authors: Bowers, Gregory A., Baldasare, Corey A., Seybold, Paul G.
• Format: Article
• Language: English
• Subjects: Agent-based models; Anions; Cellular automata; Density functional theory; Ketones; Organic chemistry
• ISSN: 0894-3230; 1099-1395
• DOI: 10.1002/poc.4592

The subject of keto‐enol equilibrium has a long history and well‐established position within physical organic chemistry. Nonetheless, one still finds numerous reports of confusing findings and questions of accuracy when dealing with its practical application. In this report, some apparently anomalous recent observations are reviewed and then reexamined using density functional theory computations and agent‐based (cellular automata) models of the keto‐enol‐anion equilibrium system. It becomes apparent that a resolution of many of the results can be achieved by taking into account the fact that although the ketone form is often present in overwhelmingly greater concentration, the enol can still contribute significantly to formation of the anion through its much greater acidity. Thus, in these cases, dissociation data assigned solely to the ketone form should in fact be recognized as representing a mixture of contributions from both the keto and the (neglected) enol form.