Interactions Between [PdX 4 ] 2- (X=Cl, Br) Dianions in Presence of Counterions

The interaction between two square palladium (II) dianions PdX (X=Cl, Br) is evaluated by crystal study and analyzed by quantum chemical means. The arrangement within the crystal between each pair of PdX neighbors is suggestive of a Pd⋅⋅⋅X noncovalent bond, which is verified by a battery of computational protocols. While the potential between these two bare dianions is computed to be highly repulsive, the introduction of even just two counterions makes this interaction attractive, as does the presence of a constellation of point charges. It is concluded that there is indeed a stabilizing Pd⋅⋅⋅X bond, but it is incapable of overcoming the strong coulombic repulsive force between two dianions. While the QTAIM, NBO, and NCI tools can indicate the presence of a noncovalent bond, they are unable to distinguish an attractive from a repulsive interaction.