Thermodynamic hydricity of small borane clusters and polyhedral closo-boranes

Abstract

Thermodynamic hydricity (HDAMeCN) determined as Gibbs free energy (∆G◦[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 [BnHn]2-, and their lithium salts Li2[BnHn] (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 (HDAMeCN = 82.1 kcal/mol) and its dianion [B2H6]2- (HDAMeCN = 40.9 kcal/mol for Li2[B2H6]) can be selected as border points for the range of borane clusters’ reactivity. Borane clusters with HDAMeCN below 41 kcal/mol are strong hydride donors capable of reducing CO2 (HDAMeCN = 44 kcal/mol for HCO2-), whereas those with HDAMeCN 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 HDAMeCN 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 HDAMeCN