Theoretical study of the redox reactivity of complex boron hydrides K2[B12H12], Cs2[B12H12], and Tl2[B10H10] and their mixed salts K2[B12H12] • KCl, Cs2[B12H12] • CsCl, and Tl2[B10H10] • KNO3

Abstract

The ability of K2[B12H12], Cs2[B12H12], and Tl2[B10H10] molecules to act as the oxidant of n-octane in the gas phase has been considered in comparison with the O2, HNO3, and KNO3 molecules. Calculations have been performed at the B3LYP/6-31G*//6-311+G* + LanL2Dz level. Notwithstanding the fact that model calculations of isolated K2[B12H12], Cs2[B12H12], and Tl2[B10H10] molecules only approximately reflect the properties of solid K2[B12H12], Cs2[B12H12], and Tl2[B10H10], such a consideration makes it possible to reveal the molecular analogue of the “salt” effect: the oxidative ability of mixed salts K2[B12H12] • KCl, Cs2[B12H12] • CsCl, and Tl2[B10H10] • KNO3, in terms of the difference of the electronic chemical potentials of the oxidant and reductant, as well as of estimated electron density transfer, turns out to be similar to the oxidative ability of pure K2[B12H12], Cs2[B12H12], and Tl2[B10H10].