Multi-center covalency: revisiting the nature of anion–π interactions

摘要: Exploring the nature of anion–π bonding by means Quantum Theory Atoms in Molecules (QTAIM) and an energy decomposition scheme on basis Interacting (IQA) theory led us to conclude that these non-classical interactions benefit from “multi-center covalency” far more than electrostatics. Comparing systems closely related covalent anion–σ complexes reveals extensive degree electron sharing between anions all atoms π-rings. Besides, binding into classical (electrostatics) (exchange–correlation) components demonstrates contrast previous reports, are local minima, if only contribution surpasses This suggests stable with atop π-rings might be prepared π-systems exchange–correlation term, such as extended π-systems, but not strong electrostatic π-receptors. conclusion is line tendency π-acids form σ-complexes character instead π-complexes.