Proton and Lithium Cations Linked to π-Electron and σ-Electron Systems: Are Such Interactions beyond or within the Definition of Hydrogen/Lithium Bond?

Abstract

MP2/aug-cc-pVTZ calculations were performed on systems containing a proton or a lithium cation located between two π-electron systems or between π-electron and σ-electron units. The proton or the lithium cation attached to the acetylene or its derivative may be treated as the Lewis acid unit while the remaining part of the complex, the π-electron species or the dihydrogen, act as the Lewis base through their π-electrons or σ-electrons, respectively. The complexes analysed here are linked by the π⋅⋅⋅H⁺ /Li⁺ ⋅⋅⋅π and π⋅⋅⋅H⁺ /Li⁺ ⋅⋅⋅σ interactions. It is discussed whether these interactions are classified as hydrogen and lithium bonds. Therefore, different definitions of the latter interactions are presented. The Electron Localization Function (ELF) and the Natural Bond Orbital (NBO) approaches were applied to analyse the above-mentioned complexes. The unique properties of interactions with the proton and with the lithium cation that occur in complexes analysed here are described.

Keywords: electron localization function (ELF); hydrogen bond; lithium bond; multi-centre covalent bond; natural bond orbital (NBO).