Thermodynamic and kinetic insights into B ₁₀ H ₁₄ and B ₁₀ H ₁₄ ²⁻

Abstract The dianion [B 10 H 14 ] 2− has attracted renewed attention due to its structural characteristics and a mercury-free synthesis route. Although its arachno structure has been reported, we explored the potential energy surface of B 10 H 14 2− to identify more stable species. Subsequent analyses included bonding evaluation, kinetic studies, and Born-Oppenheimer molecular dynamics (BO-MD) simulations. Calculations indicate that the closo -[B 10 H 10 ] 2− ⋯2H 2 complex is 21.5 kcal mol −1 more stable than the arachno structure. The complex is stable below 110 K but dissociates into closo -[B 10 H 10 ] 2− and H 2 at higher temperatures. The arachno isomer remains kinetically stable because a 30 kcal/mol activation barrier prevents its conversion. BO-MD simulations corroborate this kinetic stability, as the arachno framework is maintained during the trajectories. The effects of the solvent and the counterions were also examined and found to have a negligible influence on the relative energetics.