Journal of the American Chemical Society, Vol.124, No.17, 4910-4917, 2002
Gas-phase stability of derivatives of the closo-hexaborate dianion B6H62-
B6H62- 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 B6H62-dianion by substitution of the hydrogens with appropriate ligands, Various hexa-, tetra-, and disubstituted derivatives B6L62-, B6H2L42-, and B6H4L22- (L = F, Cl, CN, NC, or BO) are investigated with ab initio methods in detail. Four stable hexasubstituted B6H62- (L = Cl, CN, NC, or BO) and three stable B6H2L42- (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.