Metal-free dehydrogenation of amine-boranes by an N-heterocyclic carbene

The dehydrogenation of primary and secondary amine-boranes (RNH(2)·BH(3) and R(2)NH·BH(3); R = alkyl groups) was studied using the bulky N-heterocyclic carbene IPr (IPr = [(HCNDipp)C:]; Dipp = 2,6-(i)Pr(2)C(6)H(3)) as a stoichiometric dehydrogenation agent. In the case of primary amine-boranes, carbene-bound adducts IPr·BH(2)-NH(R)-BH(3) were obtained in place of the desired polymers [RNH-BH(2)](n). The secondary amine-borane (i)Pr(2)NH·BH(3) participated in dehydrogenation chemistry with IPr to afford the aminoborane [(i)Pr(2)N=BH(2)] and the dihydroaminal IPrH(2) as products. Attempts to induce H(2) elimination from the arylamine-borane DippNH(2)·BH(3) yielded a reaction mixture containing the known species IPr·BH(2)NHDipp, IPr·BH(2)NH(Dipp)-BH(3), free DippNH(2) and IPrH(2). The new hindered aryl-amine borane adduct Ar*NH(2)·BH(3) [Ar* = 2,6-(Ph(2)CH)(2)-4-MeC(6)H(2)] underwent a reaction with IPr to give IPr·BH(3) and free Ar*NH(2), consistent with the presence of a weaker N-B dative bond in Ar*NH(2)·BH(3) relative to its less hindered amine-borane analogues.