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

From National Research Council Canada

DOIResolve DOI: https://doi.org/10.1007/s00216-019-01598-4
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Name affiliation
  1. National Research Council Canada. Metrology Research Centre
FormatText
TypeArticle
Journal titleAnalytical and Bioanalytical Chemistry
ISSN1618-2642
1618-2650
Volume411
Issue8
Pages1569–1578
Subjectamine-boranes; hydrolysis; direct analysis in real time; mass spectrometry; chemical vapor generation; mechanism
Abstract
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-BuNH2·BH3 and Me2NH·BH3 were acquired under conditions that are employed in CVG (0.017–4.0 mol L−1 HCl, 0.167–0.2 mol L−1 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., R3N·BH3 + H3O+ → R3NH+ + H2OBH3). At higher acidity, N-tert-butyl, cyclotriborazane, and bis(dimethylamino)boronium were identified, for the first time, during the hydrolysis of t-BuNH2·BH3 and Me2NH·BH3, respectively. Formation of these intermediates was ascribed to a hydrolysis pathway starting with the ionization of the amine-borane, (i.e., R3N·BH3 + H3O+ → [(H2O)R3NBH2] + + H2). 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.
Publication date
PublisherSpringer
LanguageEnglish
Peer reviewedYes
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