The Large closo-Borane Dianions, BnHn2- (n = 13−17) Are Aromatic, Why Are They Unknown?

Abstract

The relative stabilities of the unknown larger closo-borane dianions B(n)()H(n)()(2)(-) (n = 13-17), were evaluated at the B3LYP/6-31G level of density functional theory by comparing the average energies, E/n, and also by the energies using the model equation: B(n)()(-)(1)H(n)()(-)(1)(2)(-) + B(6)H(10) --> B(n)()H(n)()(2)(-) + B(5)H(9) (n = 6-17). Starting with the small closo-borane, B(5)H(5)(2)(-), the sequential addition of BH groups is represented by formal transfer from B(6)H(10) to build up larger and larger clusters. Most of the energies for these sequential steps are exothermic, but not for the B(12)H(12)(2)(-) to B(13)H(13)(2)(-) and the B(14)H(14)(2)(-) to B(15)H(15)(2)(-) stages. The cumulative total energies (DeltaH(add)) of these BH group additions, based on B(5)H(5)(2)(-) as the reference zero, tend to increase with increasing cluster size. DeltaH(add) indicates that the larger unknown closo-boranes B(13)H(13)(2)(-) to B(17)H(17)(2)(-) are more stable than B(9)H(9)(2)(-), B(10)H(10)(2)(-), and B(11)H(11)(2)(-); this agrees with E/n and with Lipscomb's earlier conclusion based on the PRDDO average energies. B(13)H(13)(2)(-), B(14)H(14)(2)(-), and B(15)H(15)(2)(-) are less stable than B(12)H(12)(2)(-), which has the lowest average energy on a per vertex basis among the closo-borane dianions. However, the total DeltaH(add) treatment indicates the larger B(16)H(16)(2)(-) and B(17)H(17)(2)(-) to be favorable relative to B(12)H(12)(2)(-), because of the larger number of vertexes. The formation of B(13)H(13)(2)(-) from B(12)H(12)(2)(-) is especially unfavorable. The further formation of B(14)H(14)(2)(-) and B(15)H(15)(2)(-) via BH transfer also is endothermic. These are not the only thermodynamic difficulties in building up large closo-borane dianions beyond B(12)H(12)(2)(-). The highly exothermic disproportionation of larger and smaller closo-borane dianions, e.g., B(12+)(n)()H(12+)(n)()(2)(-) + B(12)(-)(n)()H(12)(-)(n)()(2)(-) --> 2B(12)H(12)(2)(-) (n = 1-5), also indicate possible synthetic problems in preparing larger closo-boranes with more than 12 vertexes under condition where smaller boranes are present. All the larger closo-B(n)()H(n)()(2)(-) (n = 13-17) cluster exhibit "three-dimensional aromaticity", judging from the computed Nucleus Independent Chemical Shifts (NICS), which range from -30.9 to -36.5 ppm. The trends in NICS values are similar to the variations in the bond length alternations, Deltar. Thus, the qualitative relationships between geometric and magnetic criteria of aromaticity found earlier for the smaller clusters extends to the larger closo-borane dianions, B(n)()H(n)()(2)(-) (n = 13-17).