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Keywords:

  • electrophilicity;
  • kinetics;
  • linear free-energy relationships;
  • nucleophilicity;
  • solvent effects
Thumbnail image of graphical abstract

Solvent matters: Cations are reference substrates in the equation log k=s(E+N); neglect of solvent effects (see picture; TS=transition state) on their electrophilicity (E) leads to unreliable values of the nucleophilicity (N) and slope (s) parameters that characterize nucleophiles (k is the rate constant). Consequently, these parameters are not recommended for a general scale of nucleophilicity as suggested by Mayr and co-workers.