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].