Influence of metal ion on chelate-aryl stacking interactions
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abstract
AbstractCCSD(T)/CBS and DFT methods are employed to study the stacking interactions of acetylacetonatetype (acactype) chelates of nickel, palladium, and platinum with benzene. The strongest chelatearyl stacking interactions are formed by nickel and palladium chelate, with interaction energies of 5.75 kcal mol1 and 5.73 kcal mol1, while the interaction of platinum chelate is weaker, with interaction energy of 5.36 kcal mol1. These interaction energies are significantly stronger than stacking of two benzenes, 2.73 kcal mol1. The strongest nickel and palladium chelatearyl interactions are with benzene center above the metal area, while the strongest platinum chelatearyl interaction is with the benzene center above the C2 atom of the acactype chelate ring. These preferences arise from very different electrostatic potentials above the metal ions, ranging from very positive above nickel to slightly negative above platinum. While the differences in electrostatic potentials above metal atoms cause different geometries with the most stable interaction among the three metals, the dispersion (correlation energy) component is the largest contribution to the total interaction energy for all three metals.
