The nature of the Na⋯B bond, in the recently synthesized NaBH 3 - adduct, is analyzed on the light of the Na- propensity to polarize along the bond axis as a consequence of the electric field produced by the BH3 fragment. The observed induced polarization has two consequences: (i) the energetic stabilization of the Na- , and (ii) the split of its valence electrons into two opposite lobes along the bond axis. Additionally, an analysis of the electron localization is presented using the information content of the correlated conditional pair density that reveals a significant delocalization between one lobe of the polarized Na- anion and the BH3 fragment at the equilibrium distance. Our findings reported here complement previous works on this system.
