Abstract
The fluoride affinities of fluorinated alanes, AlH m F 3− m ( m = 1–3) were measured using energy-resolved collision-induced dissociation of fluorinated aluminate anions. The AlH m F 4− m − anions were formed by reaction of dimethylethylamine-alane with fluoride ion and F 2. From the measured bond dissociation energies, the fluoride affinities of fluorinated alanes are determined to be 93.2 ± 3.1, 97.5 ± 4.0, and 108.6 ± 3.7 kcal/mol for m = 3, 2, and 1, respectively. The fluoride affinities are in good agreement with the theoretical calculations at the CCSD(T)/CBS and B3LYP/6-31 + G* levels of theory. The increased Lewis acidity of more fluorinated alanes is attributed to increased positive charge density on the aluminum.
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