Abstract

It is here reported that the NaBH3- cluster exhibits a Na.B one-electron bond, a well-established type of electron-deficient bonding in the literature. The topological analysis of the electron localization function, at the correlated level, reveals that Na-, when approaching the bonding distance, fairly distributes its valence electron pair between two lobes. One of these electrons is used to bond with BH3, which participates through its boron empty p-orbital. Furthermore, the bonding situation of LiBH3-, KBH3-, MgBH3, and CaBH3 global minima structures are similar to that of NaBH3-, extending the family of these new one-electron bond systems with biradicaloid character.