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Keywords:

  • ab initio calculations;
  • computational chemistry;
  • Marcus theory;
  • nucleophilic substitution;
  • transition states
Thumbnail image of graphical abstract

A better approach to ambident reactivity: The principle of hard and soft acids and bases (HSAB) cannot rationalize the reactivities of even the prototypical ambident nucleophiles shown in the picture. Marcus theory, which describes activation energies by a combination of intrinsic and thermodynamic terms, is a superior alternative.