Application of direct analysis in real time to the study of chemical vapor generation mechanisms: identification of intermediate hydrolysis products of amine-boranes.

In order to elucidate controversial results emerging in chemical vapor generation (CVG) for trace element determination, we conducted a series of experiments devoted to the identification of intermediates formed by acid hydrolysis of amine-boranes. For the first time, direct analysis in real time coupled with high-resolution mass spectrometry (DART-Orbitrap) was applied for detection of this class of compounds. Mass spectra of both solid amine-boranes and their aqueous solutions (pH ~ 8, no hydrolysis) were acquired for understanding their ionization pathway. Mass spectra of aqueous solutions of t-BuNH·BH and MeNH·BH were acquired under conditions that are employed in CVG (0.017-4.0 mol L HCl, 0.167-0.2 mol L borane reagent). The results disclose a reactivity driven by pH of amine-boranes undergoing hydrolysis. At low acidity, the hydrolysis proceeds according to the currently accepted displacement mechanisms (i.e., RN·BH + HO → RNH + HOBH). At higher acidity, N-tert-butyl, cyclotriborazane, and bis(dimethylamino)boronium were identified, for the first time, during the hydrolysis of t-BuNH·BH and MeNH·BH, respectively. Formation of these intermediates was ascribed to a hydrolysis pathway starting with the ionization of the amine-borane, (i.e., RN·BH + HO → [(HO)RNBH] + H). The new evidence explains the anomalous behavior observed in CVG by amine-borane derivatization, and updates the currently accepted mechanisms for the acid hydrolysis of amine-boranes. Graphical Abstract.