Thermodynamic Hydricity of Small Borane Clusters and Polyhedral closo-Boranes †.

Thermodynamic hydricity (HDA^MeCN) determined as Gibbs free energy (ΔG°[H]⁻) of the H⁻ detachment reaction in acetonitrile (MeCN) was assessed for 144 small borane clusters (up to 5 boron atoms), polyhedral closo-boranes dianions [B_nH_n]²⁻, and their lithium salts Li₂[B_nH_n] (n = 5–17) by DFT method [M06/6-311++G(d,p)] taking into account non-specific solvent effect (SMD model). Thermodynamic hydricity values of diborane B₂H₆ (HDA^MeCN = 82.1 kcal/mol) and its dianion [B₂H₆]²⁻ (HDA^MeCN = 40.9 kcal/mol for Li₂[B₂H₆]) can be selected as border points for the range of borane clusters' reactivity. Borane clusters with HDA^MeCN below 41 kcal/mol are strong hydride donors capable of reducing CO₂ (HDA^MeCN = 44 kcal/mol for HCO₂⁻), whereas those with HDA^MeCN over 82 kcal/mol, predominately neutral boranes, are weak hydride donors and less prone to hydride transfer than to proton transfer (e.g., B₂H₆, B₄H₁₀, B₅H₁₁, etc.). The HDA^MeCN values of closo-boranes are found to directly depend on the coordination number of the boron atom from which hydride detachment and stabilization of quasi-borinium cation takes place. In general, the larger the coordination number (CN) of a boron atom, the lower the value of HDA^MeCN. [ABSTRACT FROM AUTHOR]