Dianionic tetraborates do exist as stable entities.

To date, B(6)H(6)(2-) and some of its derivatives are the smallest members of the closo-borates that have been synthesized and analyzed in condensed phases. In contrast, no stable dianionic tetraborate has yet been observed, either in solution or solids or in the gas phase. In this work, the gas-phase stability of dianionic tetraborates B(4)X(4)(2-) (X = H, CN, NC, or BO) is investigated with ab initio methods. For this objective, the geometries of the dianions are optimized, the electronic stability is tested, and various fragmentation channels are studied. In agreement with previous examinations, tetrahedral isomers of all examined tetraborates have been found to represent geometrically stable isomers and to exhibit a triplet electronic ground state. However, these isomers are electronically unstable, i.e., their additional electrons are not bound. Furthermore, new D(2)(d)()-symmetric isomers of B(4)X(4)(2-) (X = H, CN, NC, or BO) have been identified that have a closed-shell singlet ground state and are lower in energy than their tetrahedral counterparts. Moreover, B(4)(CN)(4)(2-) and B(4)(BO)(4)(2-) represent stable gas-phase dianions and are predicted to be observable in suitable experiments. The electronic properties and geometries of these dianions are discussed in detail and explained in terms of the electrostatic repulsion of the excess electrons and the aromaticity of the dianions.