The critical size of hydrogen-bonded alcohol clusters as effective Brønsted bases in solutions

Sun Young Park, Taeg Gyum Kim, Manjaly J. Ajitha, Kijeong Kwac, Young Min Lee, Heesu Kim, Yousung Jung*, Oh Hoon Kwon

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

13 Scopus citations

Abstract

The alkyl oxonium ion, which is a protonated alcohol, has long been proposed as a key reaction intermediate in alcohol dehydration. Nonetheless, the dynamics and structure of this simple but important intermediate species have not been adequately examined due to the transient nature of the oxonium ion. Here, we devised a model system for the key step in the alcohol dehydration reaction, in which a photoacid transfers a proton to alcohols of different basicity in the acetonitrile solvent. Using time-resolved spectroscopy and computation, we have found that the linkage of at least two alcohol molecules via hydrogen bonding is critical for their enhanced reactivity and extraction of the proton from the acid. This finding addresses the cooperative role of the simplest organic protic compounds, namely alcohols, in nonaqueous acid-base reactions.

Original languageEnglish (US)
Pages (from-to)24880-24889
Number of pages10
JournalPhysical Chemistry Chemical Physics
Volume18
Issue number36
DOIs
StatePublished - 2016

Bibliographical note

Funding Information:
This work was supported by the Institute for Basic Science (IBS-R020-D1), Korea. O. H. K., Y. M. L., and H. K. also received support from NRF Korea funded by the Ministry of Science, ICT and Future Planning (MSIP) (2014R1A1A1008289). K. K. and Y. J. acknowledge support from the KUSTAR-KAIST Institute, KAIST, Korea. We thank Dr Johan Schmidt for helpful discussions.

Publisher Copyright:
© 2016 the Owner Societies.

ASJC Scopus subject areas

  • General Physics and Astronomy
  • Physical and Theoretical Chemistry

Fingerprint

Dive into the research topics of 'The critical size of hydrogen-bonded alcohol clusters as effective Brønsted bases in solutions'. Together they form a unique fingerprint.

Cite this