Pairing and unpairing electron densities in organic systems: two-electron three center through space and through bonds interactions

Two-electron three-center bonding interactions in organic ions like methonium (CH5(+)), ethonium (C2H7(+)), and protonated alkanes n - C4H11(+) isomers (butonium cations) are described and characterized within the theoretical framework of the topological analysis of the electron density decomposition into its effectively paired and unpaired contributions. These interactions manifest in some of this type of systems as a concentration of unpaired electron cloud around the bond paths, in contrast to the well known paradigmatic boron hydrids in which it is not only concentrated close to the atomic nucleus and the bond paths but out of them and over the region defined by the involved atoms as a whole. This result permits to propose an attempt of classification for these interactions based in such manifestations. In the first type, it is called as interactions through bonds and in the second type as interactions through space type.