Alcohol Dimer is Requisite to Form an Alkyl Oxonium Ion in the Proton Transfer of a Strong (Photo)Acid to Alcohol. Issue 13 (28th January 2016)

• Record Type: Journal Article
• Authors: Park, Sun‐Young; Lee, Young Min; Kwac, Kijeong; Jung, Yousung; Kwon, Oh‐Hoon
• Is Part Of: Chemistry. Volume 22:Issue 13(2016)
• Page Start: 4340
• Page End: 4344
• Publication Date: 2016-01-28
• Subjects: alcohols -- dehydration -- hydrogen bonds -- proton transport -- time-resolved spectroscopy; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201503948
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: Alcohols, the simplest amphiprotic organic compounds, can exhibit either acidic or basic behavior by donating or accepting a proton. In this study, proton dissociation of a model photoacid in solution is explored by using time‐resolved spectroscopy, revealing quantitatively for the first time that alcohol acts as a Brønsted base because of H‐bonded cluster formation to enhance the reactivity. The protonated alcohol cluster, the alkyl oxonium ion, can be regarded as a key reaction intermediate in the well‐established alcohol dehydration reaction. This finding signifies, as in water, the cooperativity of protic solvent molecules to facilitate nonaqueous acid–base reactions. Abstract : Dimer delights : The formation of an alkyl oxonium ion, a long‐proposed intermediate in alcohol dehydration, is studied by time‐resolved fluorescence quenching of a strong Brønsted photoacid. The collaboration of two alcohol molecules is critical to enhance the reactivity and extract the proton from the acid.