B(6)H(6)(2-) does not represent a stable gas-phase dianion, but emits spontaneously one of its excess electrons in the gas phase. In this work we address the question whether small stable gas-phase dianions can be constructed from the parent B(6)H(6)(2-) dianion by substitution of the hydrogens with appropriate ligands. Various hexa-, tetra-, and disubstituted derivatives B(6)L(6)(2-), B(6)H(2)L(4)(2-), and B(6)H(4)L(2)(2-) (L = F, Cl, CN, NC, or BO) are investigated with ab initio methods in detail. Four stable hexasubstituted B(6)L(6)(2-) (L = Cl, CN, NC, or BO) and three stable B(6)H(2)L(4)(2-) (L = CN, NC, or BO) gas-phase dianions could be identified and predicted to be observable in the gas phase. The trends in the electron-detachment energies depending on various ligands are discussed and understood in the underlying electrostatic pattern and the electronegativities of the involved elements.

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.

2002 theory, structure theory, structure C 1000 -001Gas-Phase Stability of Derivatives of the closo-Hexaborate Dianion B 6 H 2− 6 .-B 6 L 6 2− (L: -Cl, -CN, -NC, -BO) and B 6 H 2 R 4 2− (R: -CN, -NC, -BO) gas phase dianions are identified and predicted by quantum chemical ab initio Hartree-Fock-SCF and perturbation theory (MP2) calculations to be observable in the gas phase. The equilibrium structures of the hexasubstituted dianions possess O h symmetry and the trans-isomers of the tetrasubstituted species exhibit D 4h symmetry. -(ZINT, N.; DREUW, A.; CEDERBAUM, L. S.; J.