Reid, Joshua Elias Samuel James, Aquino, Pedro H. G., Walker, Adam J. et al. (2 more authors) (2019) Statistical thermodynamics unveils how ions influence an aqueous Diels-Alder reaction. ChemPhysChem. pp. 1538-1544. ISSN 1439-4235
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 reactant, while rate-enhancing salts exhibit stronger affinity to the transition state.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 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. |
Keywords: | Diels-Alder reaction,Kirkwood-Buff theory,salts,statistical thermodynamics,water |
Dates: |
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Institution: | The University of York |
Academic Units: | The University of York > Faculty of Sciences (York) > Chemistry (York) |
Depositing User: | Pure (York) |
Date Deposited: | 13 Mar 2019 10:10 |
Last Modified: | 26 Jan 2025 00:13 |
Published Version: | https://doi.org/10.1002/cphc.201900024R1 |
Status: | Published |
Refereed: | Yes |
Identification Number: | 10.1002/cphc.201900024R1 |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:143606 |
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Filename: ChemPhysChem_Revised_Final_12_03_2019.pdf
Description: ChemPhysChem Revised Final 12 03 2019