A series of formal donor-acceptor adducts of aminoborane (H2BNH2) and its N-substituted analogues (H2BNRR') were prepared: LB-H2BNRR'(2)-BH3 (LB = DMAP, IPr, IPrCH2 and PCy3; R and R' = H, Me or tBu; IPr = [(HCNDipp)(2)C:] and Dipp = 2,6-iPr(2)C(6)H(3)). To potentially access complexes of molecular boron nitride, LB-BN-LA (LA = Lewis acid), preliminary dehydrogenation chemistry involving the parent aminoborane adducts LB-H2BNH2-BH3 was investigated using [Rh(COD)Cl](2), CuBr, and NiBr2 as dehydrogenation catalysts. In place of isolating the intended dehydrogenated BN donor-acceptor complexes, the formation of borazine was noted as a major product. Attempts to prepare the fluoroarylborane-capped aminoborane complexes, LB-H2BNH2-B (C6F5)(3), are also described.