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

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


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.

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