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Solvation Accounts for the Counterintuitive Nucleophilicity Ordering of Peroxide Anions
Author(s) -
Mayer Robert J.,
Tokuyasu Takahiro,
Mayer Peter,
Gomar Jérôme,
Sabelle Stéphane,
Mennucci Benedetta,
Mayr Herbert,
Ofial Armin R.
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201707086
Subject(s) - chemistry , nucleophile , solvation , reaction rate constant , peroxide , polarizable continuum model , deprotonation , aqueous solution , solvent , ion , computational chemistry , solvent effects , medicinal chemistry , photochemistry , kinetics , organic chemistry , catalysis , physics , quantum mechanics
The nucleophilic reactivities ( N , s N ) of peroxide anions (generated from aromatic and aliphatic peroxy acids or alkyl hydroperoxides) were investigated by following the kinetics of their reactions with a series of benzhydrylium ions (Ar 2 CH + ) in alkaline aqueous solutions at 20 °C. The second‐order rate constants revealed that deprotonated peroxy acids (RCO 3 − ), although they are the considerably weaker Brønsted bases, react much faster than anions of aliphatic hydroperoxides (ROO − ). Substitution of the rate constants of their reactions with benzhydrylium ions into the linear free energy relationship lg k = s N ( N + E ) furnished nucleophilicity parameters ( N , s N ) of peroxide anions, which were successfully applied to predict the rates of Weitz–Scheffer epoxidations. DFT calculations with inclusion of solvent effects by means of the Integral Equation Formalism version of the Polarizable Continuum Model were performed to rationalize the observed reactivities.