Gas-phase stability of derivatives of the closo-hexaborate dianion B(6)H(6)(2-).
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.
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Theoretische Chemie, Physikalisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 229, 69120 Heidelberg, Germany.
Dreuw
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Cederbaum
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