Scrutinizing ion-π and ion-σ interactions using the noncovalent index and energy decomposition analysis

The nature and origin of ion-pi and ion-sigma interactions has been systematically investigated using dispersion-corrected density functional theory and the recently developed noncovalent interaction (NCI) method. A detailed analysis of these interactions is performed with the aim to identify the requirements that have to be fulfilled by the molecular system for strong ion-ligand interactions. Interestingly, our results indicate that aliphatic systems, such as cyclohexane, can interact as strong as aromatic ones with both cations and anions, despite of having a negligible quadrupole moment. In fact, cyclohexane binds anions stronger than benzene itself but slightly weaker that hexafluorobenzene. The NCI method reveals that the interaction between the ions and three C-H bonds of the saturated fragment are responsible for the surprisingly strong ion-sigma interaction. A weakening of the ion-sigma interactions is observed in the order: Li+ > F- > Na+ Cl- > Br- approximate to K+. In addition, a complete Ziegler-Rauk type energy decomposition analysis has been carried out in order to reveal the origins of the thermodynamic driving force for complex formations. The electron density deformation upon complex formation has been scrutinized with a complementary NOCV analysis allowing the identification of molecular orbital interaction contributions to the stabilization. Based on these analysis, it is shown that the formally anion-pi interaction is rather an anion-sigma* interaction. (C) 2014 Elsevier B.V. All rights reserved.