Geminal Diol Formation from the Interaction of a Ketone with Water in the Gas Phase: Structure and Reactivity of Cyclooctanone-(H2O)1,2 Clusters

• Published in: The journal of physical chemistry letters 2021-12, Vol.12 (51), p.12419-12425
• Main Authors: Burevschi, Ecaterina, Peña, Isabel, Sanz, M. Eugenia
• Format: Article
• Language: English
• Subjects: Physical Insights into Chemistry, Catalysis, and Interfaces
• ISSN: 1948-7185; 1948-7185
• DOI: 10.1021/acs.jpclett.1c03493

The hydration of ketones is known to occur in condensed phases, but it is not considered to be favorable in the gas phase due to restricted water content. We report the first evidence of geminal diol formation upon ketone hydration in the gas phase, obtained through the investigation of the interactions of cyclooctanone with water using broadband rotational spectroscopy. Oxygen-atom exchange between water and cyclooctanone was observed for two isomers of cyclooctanone-H2O and two isomers of cyclooctanone-(H2O)2. All complexes were unambiguously identified from the analysis of the rotational spectrum of the parent species and all their 13C and 18O isotopologues, and their heavy-atom substitution and effective structures were determined as well as their binding interactions. The production of gem-diols from gas-phase hydration of ketones has implications for atmospheric chemistry and opens a new channel for secondary aerosol formation.