Anion⋅⋅⋅Anion Attraction in Complexes of MCl3− (M=Zn, Cd, Hg) with CN−. Issue 11 (5th May 2020)

• Record Type: Journal Article
• Authors: Wysokiński, Rafał; Zierkiewicz, Wiktor; Michalczyk, Mariusz; Scheiner, Steve
• Is Part Of: Chemphyschem. Volume 21:Issue 11(2020)
• Page Start: 1119
• Page End: 1125
• Publication Date: 2020-05-05
• Subjects: atoms in molecules -- energy decomposition -- molecular electrostatic potential -- π-hole -- solvent effects; Chemistry, Physical and theoretical -- Periodicals; 541.05
• DOI: 10.1002/cphc.202000206
• Languages: English
• ISSNs: 1439-4235

Abstract

Abstract: High‐level ab initio calculations show that the MCl3 − anions comprising Group 2B M atoms Zn, Cd, and Hg form a stable complex with the CN − anion, despite the like charge of the two ions. The complexation occurs despite a negative π‐hole region above the M atom of MCl3 − . The dimerization distorts the planar geometry of MCl3 − into a pyramidal shape which reduces the negative potential above the M atom, facilitating a close approach of the two anions, with R(M⋅⋅⋅C)∼2 Å, and an overall attractive electrostatic attraction within the dimer. In the gas phase, this dimer is less stable than the pair of separated ions by some 30 kcal/mol. However, the dissociation must surmount an energy barrier of roughly 25 kcal/mol which occurs at an intermolecular distance of 4 Å. In aqueous solution, the dimerization process is exothermic and barrier‐free, with a binding energy in the 11–18 kcal/mol range. Abstract : Complexation between two anions CN − and MCl3 − (M=Zn, Cd, Hg) occurs despite a negative π‐hole region above the M atom of MCl3 − .