By the same authors

From the same journal

Statistical thermodynamics unveils how ions influence an aqueous Diels-Alder reaction

Research output: Contribution to journalArticle

Published copy (DOI)

Author(s)

Department/unit(s)

Publication details

JournalChemPhysChem
DateSubmitted - 7 Jan 2019
DateAccepted/In press - 13 Mar 2019
DateE-pub ahead of print (current) - 23 Apr 2019
Volume20
Number of pages8
Early online date23/04/19
Original languageEnglish

Abstract

The kinetics of Diels-Alder (DA) reactions in water has been known to be altered by salts for a long time. Yet the question how salts influence the reaction rate, either as rate-enhancing or rate-reducing additives, has so far remained unresolved. Conflicting hypotheses involve (i) indirect salt contributions through the modulation of internal pressure and (ii) making (or breaking) of the so-called “water-structure” by salts that strengthen (or weaken) the hydrophobic effect. In contrast to the qualitative nature of these hypotheses, here we answer this question quantitatively through a combination of transition state theory and fluctuation adsorption-solvation theory (FAST) using the DA reaction between anthracene-9-carbinol and N-ethylmaleimide as an example. We show that rate enhancement is driven by the salting out of the hydrophobic reagent, while rate-enhancing salts exhibit stronger affinity to the transition state.

Bibliographical note

© 2019 Wiley-VCH. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details.

Discover related content

Find related publications, people, projects, datasets and more using interactive charts.

View graph of relations