Alkaline-Earth Derivatives of the Reactive [HB(CF)] Anion.

The β-diketiminato magnesium amidoboranes [HC{(Me)CNDipp}Mg(NMeBHNMe·BH)] and [HC{(t-Bu)CNDipp}Mg(NMe·BH)] are readily converted to the corresponding derivatives of the [HB(CF)] anion by treatment with B(CF). The bis(borohydride) derivatives of the heaviest alkaline-earth elements, strontium and barium, may be similarly synthesized by reaction of strontium or barium dimethylamidoboranes and B(CF) and by metathesis reactions of either SrI or BaI and 2 molar equiv of K(HB(CF)). The strontium and barium compounds have been fully characterized in solution and in the solid state as the respective tris(diethyl ether) and tetrakis(tetrahydrofuran) adducts. The magnesium compound [HC{(Me)CNDipp}Mg(HB(CF))] has been applied to the catalytic hydroboration of i-PrN═C═N-i-Pr with HBpin. In contrast to carbodiimide hydroboration catalyzed by the corresponding β-diketiminato magnesium hydride, which results in the exclusive production of the monoborylated amidine, use of the [HB(CF)] derivative provides the product of bis-borylation, the aminal HC(N{Bpin}i-Pr), under mild conditions. A series of stoichiometric reactions highlight that, while this reactivity is likely to be primarily magnesium mediated, B(CF) plays a vital role both in the delivery of reactive hydride and through the Lewis acid activation of the heteroallene substrate and various reactive intermediates.