Optimized Structures and Relative Stabilities of the Carboranes from Ab Initio Calculations

Abstract

AbstractAb initio calculations at the STO‐3G level were performed on almost all of the possible isomers for the entire series of closo‐carboranes, C2Bn‐2Hn, 5 ⩽ n ⩽ 12. Geometry optimizations using the gradient method were also included in all calculations. We report here the relative energies obtained for the various isomers as well as the optimized structures. These calculations confirm our previous predictions of relative stabilities obtained from topological charge stabilization. Comparisons of our structures with those from experimental data provide us with a measure of reliability for bond distances obtained using ab initio SCF MO calculations at the STO‐3G level. Results from the geometry optimization substantiated the experimentally known fluxional behavior of the 8 and 11 atom polyhedra.