Ionic Liquid Facilitated Dehydrogenation of tert-Butylamine Borane.

Abstract

The current work reports ionic liquid (IL) facilitated dehydrogenation of tert-butylamine borane (TBAB) at 90 and 105 °C. For the screening of potential IL solvent, solubility predictions of TBAB in ILs were performed by the conductor-like screening model segment activity coefficient (COSMO-SAC) model. The COSMO-SAC model predicted a logarithmic infinite dilution activity coefficient of −6.66 and −7.31 for TBAB in 1-butyl-3-methylimidazolium acetate [BMIM][OAc] and trihexyl(tetradecyl)phosphonium bis(2,4,4-trimethylpentyl)phosphinate [TDTHP][Phosph], respectively. Hydrogen (1.95 equiv) was seen to release from TBAB/[BMIM][OAc] at 105 °C, whereas TBAB/[TDTHP][Phosph] produced 1.63 equiv of hydrogen after 360 min of dehydrogenation. The proton nuclear magnetic resonance (1H NMR) characterization of TBAB/IL systems revealed the structural integrity of ILs during dehydrogenation. Further characterization through the boron NMR (11B NMR) technique disclosed the time-resolved formation and stability of the starting compound, intermediate boron moieties, and product distribution. The 11B NMR characterization also revealed the fact that the TBAB/[TDTHP][Phosph] mixture dehydrogenates via bimolecular addition of TBAB by forming borohydride anion (−BH4–). It was seen to oligomerize with the subsequent addition of TBAB in the oligomer chain. For the TBAB/[BMIM][OAc] system, the 11B NMR characterization could not identify the borohydride anion but confirmed a faster formation of the B=N moiety when compared to the TBAB/[TDTHP][Phosph] system. On the basis of the NMR characterization, IL-facilitated dehydrogenation mechanism of TBAB is proposed.