Realization of Lewis Basic Sodium Anion in the NaBH₃ ^- Cluster

We report a Na:^- →B dative bond in the NaBH₃ ^- cluster, which was designed on the principle of minimum-energy rupture, prepared by laser vaporization, and characterized by a synergy of anion photoelectron spectroscopy and electronic structure calculations. The global minimum of NaBH₃ ^- features a Na-B bond. Its preferred heterolytic dissociation conforms with the IUPAC definition of dative bond. The lone electron pair revealed on Na and the negative Laplacian of electron density at the bond critical point further confirm the dative nature of the Na-B bond. This study represents the first example of a Lewis adduct with an alkalide as the Lewis base.