Metal-π Interactions in Light of Geometry-Corrected Statistical Analysis

Statistical analysis on metal-pi interactions has been performed, and a geometrical correction, named as offset correction, has been incorporated into the analysis to nullify the geometrical bias to understand the geometrical preference for this interaction. The population distributions of these interactions before and after offset correction with respect to the offset from the centroid of the benzenoid ring are completely different. In the cases of alkali metal-pi interactions, the population is maximum at offset zero or near zero. However, in the case of transition metal-pi interactions, the offset for the maximum population is found near the carbon atom of the benzenoid ring. Interestingly, alkaline earth metals, which lie in between the alkali and transition metals in the periodic table, behave in between these two metals when metal-pi interaction geometry is concerned.