Anion-pi Interactions Involving [MXn]m- Anions: A Comprehensive Theoretical Study

Abstract

[eng] In this manuscript we perform a systematic study on the geometric and energetic features of anion-π complexes, wherein the anion is a metal complex of variable shapes and charges. Such a study is lacking in the literature. For the calculations we used the ab initio RI‐MP2/def2‐TZVPP level of theory. A search in the Cambridge Structural Database (CSD) provides the experimental starting point that inspired the subsequent theoretical study. The influence of [MXn]m− on the anion-π interaction was analyzed in terms of energetic, geometric, and charge transfer properties and Bader′s theory of "atom‐in‐molecules" (AIM). The binding energy depends on the coordination index, geometric features and different orientations adopted by the metallic anion. The binding mode resembling a stacking interaction for linear, trigonal planar and square‐planar anions is the most favorable. For tetrahedral and octahedral anions the most favorable orientation is the one with three halogen atoms pointing to the ring.