ChemInform Abstract: Gas‐Phase Stability of Derivatives of the closo‐Hexaborate Dianion B₆H^2‐₆.

Abstract

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.

Properties of gaseouscloso-[B6X6]2−dianions (X = Cl, Br, I)

“…[B 6 F 6 ] 2À is experimentally unknown. In agreement with previous computational investigations, 65,66 we calculated this dianion to be electronically unstable, see represents a particularly interesting case because it is very slightly electronically unstable (positive VDE but slightly negative ADE). The ability to observe the electronically unstable [B 6 Cl 6 ] 2À experimentally must result from the kinetic trapping of the excess electron (similar behavior has been observed for [C 60 ] 2À ) 67 due to the repulsive Coulomb barrier (RCB).…”

Self-doping of molecular quantum-dot cellular automata: mixed valence zwitterions

“…Bond lengths between axial B and equatorial B atoms are 1.710 and 1.735 A ˚, obtained at the ROHF level, which is in agreement with Zint et al's calculation of CN substituted species. 22 Four equatorial B atoms form a rhombus with a lateral length of 1.727 A ˚.…”

“…2 requires a moiety in the cell center which is doubly charged. The recently-shown stability of gas-phase multiply charged anions (MCAs) [21][22][23][24] may provide an important element in creating neutral molecular QCA. The research field of MCAs in the gas phase received great impetus since the experimental observation of small MCAs in 1990.…”

“…The research field of MCAs in the gas phase received great impetus since the experimental observation of small MCAs in 1990. 25 A large number of experimental 26,27 and theoretical studies 21,22 have established the existence of MCAs in the gas phase. Kalcher and Sax have written a detailed review of MCAs.…”

“…Recent studies have pointed out that, even though the closo-hexoborate dianion B 6 H 6 2À is not stable in the gas phase, some of its derivatives are. For example, B 6 L 6 2À and B 6 H 2 L 4 2À (L = BO, CN or NC) are stable in the gas phase, according to the ab initio study of Zint et al 22 The stability of these derivatives, as explained by these authors, comes from the extra molecular space provided by the diatomic pseudohalogen ligands-the larger space allows the distribution of the extra electrons across a bigger volume, thus reducing the Coulomb repulsion significantly. We here consider the possibility Fig.…”