TY - JOUR
T1 - Geminal Diol Formation from the Interaction of a Ketone with Water in the Gas Phase: Structure and Reactivity of Cyclooctanone-(H2O)1,2 Clusters
AU - Burevschi, Cate
AU - Pena Calvo, Isabel Pena
AU - Sanz, Maria
N1 - Funding Information:
This research was funded by EU FP7 (Marie Curie Grant No. PCIG12-GA-2012-334525), King’s College London, and EPSRC (EP/N509498/1). The authors thank Dr. A. Birkbeck from Firmenich for providing the sample of cyclooctanone and acknowledge the use of the research computing facility at King’s College London, Rosalind ( https://rosalind.kcl.ac.uk ).
Publisher Copyright:
© 2021 American Chemical Society
PY - 2021/12/23
Y1 - 2021/12/23
N2 - 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-H
2O and two isomers of cyclooctanone-(H
2O)
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.
AB - 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-H
2O and two isomers of cyclooctanone-(H
2O)
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.
UR - http://www.scopus.com/inward/record.url?scp=85122394956&partnerID=8YFLogxK
U2 - 10.1021/acs.jpclett.1c03493
DO - 10.1021/acs.jpclett.1c03493
M3 - Article
SN - 1948-7185
VL - 12
SP - 12419
EP - 12425
JO - Journal of physical chemistry letters
JF - Journal of physical chemistry letters
IS - 51
ER -