Abstract
Solid-state decomposition of the dihydrogen-bonded complex LiBH 4 ·TEA (TEA: triethanolamine) into a covalent material was probed via 11B MAS NMR and FT-IR spectroscopies, as well as single-crystal and powder X-ray diffraction and optical microscopy. Based on variable-temperature kinetic analysis and H/D exchange experiments, H 2 loss appears to occur via rate-limiting proton transfer from the TEA’s OH groups to the BH 4 – anions at the reactant/product interface. The activation parameters ΔH ‡=84±10 kJ/mol and ΔS ‡=−70±26 J/(mol K) are comparable to those found for neutral aqueous hydrolysis of BH 4 −, suggesting similar mechanisms for the solid and solution decompositions.
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