Anions as Lewis Acids in Noncovalent Bonds

Abstract

AbstractThe ability of an anion to serve as electron‐accepting Lewis acid in a noncovalent bond is assessed via DFT calculations. NH3 is taken as the common base, and is paired with a host of ACln− anions, with central atom A=Ca, Sr, Mg, Te, Sb, Hg, Zn, Ag, Ga, Ti, Sn, I, and B. Each anion reacts through its σ or π‐hole although the electrostatic potential of this hole is quite negative in most cases. Despite the contact between this negative hole and the negative region of the approaching nucleophile, the electrostatic component of the interaction energy of each bond is highly favorable, and accounts for more than half of the total attractive energy. The double negative charge of dianions precludes a stable complex with NH3.