Mono- and di-cationic hydrido boron compounds.

Brønsted acid HNTf2 (Tf = SO2CF3) mediated dehydrogenative hydride abstraction from (L(1))BH3 () and (L(2))BH3 () (L(1) = IPrCH2 = 1,3-(2,6-di-isopropylphenyl)imidazol-2-methylidene (); L(2) = SIPrCH2 = 1,3-(2,6-di-isopropylphenyl)imidazolidin-2-methylidiene ()) affords thermally stable hydride bridged mono-cationic hydrido boron compounds [{(L(1))BH2}2(μ-H)](NTf2) () and [{(L(2))BH2}2(μ-H)](NTf2) (). Furthermore, hydride abstraction yields di-cationic hydrido boron compounds [{(L(1))BH}2(μ-H)2](NTf2)2 () and [{(L(2))BH}2(μ-H)2](NTf2)2 (). Unique cationic boron compounds with CH2BH2(μ-H)BH2CH2 ( and ) and CH2BH(μ-H)2BHCH2 ( and ) moieties feature a 3c-2e bond and have been fully characterized. Interesting electronic and structural features of compounds are analysed using spectroscopic, crystallographic, and computational methods.