Catalytic Potential of [B12X11]2- (X = F, Cl, Br, I, CN) Dianions.

Abstract

Dodecaborate anions ([B12H12]2-) and their derivatives where hydrogen atoms are replaced by halogen, pseudohalogen, or superhalogen moieties belong to a class of very stable species, even in the gas phase. Their stability is attributed to Wade's electron counting rule that requires n + 1 pairs of skeletal electrons, n being the number of boron atoms. Consequently, [B12X11]2- (X = H, F, Cl, Br, I, CN) dianions that carry one more electron than needed to satisfy Wade's rule should not be stable, assuming that the rule applies to fragments as well. While this is the case for X = H, we show that [B12X11]2- (X = F, Cl, Br, I, CN) dianions are stable with the second electron in [B12(CN)11]2- bound by as much as 3.17 eV. More importantly, the stability of these dianions is found to have a significant effect on the activation of gas molecules such as CO2 and N2, providing a path toward the development of new catalysts.