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Mechanism of generation of volatile hydrides of trace elements by aqueous tetrahydroborate(III). Mass spectrometric studies on reaction products and intermediates

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DOIResolve DOI: https://doi.org/10.1021/ac061962c
AuthorSearch for: ; Search for: 1ORCID identifier: https://orcid.org/0000-0002-2377-2615; Search for: 1ORCID identifier: https://orcid.org/0000-0002-3349-5535; Search for: 1
Affiliation
  1. National Research Council Canada. NRC Institute for National Measurement Standards
FormatText, Article
Abstract
The mechanism of generation of volatile metal/metalloid hydrides by derivatization with borane complexes is presented. This reaction has been employed for ultratrace element analysis since 1972 and has been the source of much controversy in regard to the reaction mechanism. Here we investigated this derivatization by using As(III), Sb(III), Bi(III), MeAsO(OH)2, and Me2AsO(OH) as model analytes and NaBH4, NaBD4, tert-BuNH2BH3, and Me2NHBH3 as borane reagents. The identification of reaction products and intermediates observed under various reaction conditions was performed by gas chromatography/mass spectrometry and electrospray ionization mass spectrometry. An alternative reaction model, based on the formation of analyte−borane complex (ABC) intermediates, is able to reconcile all the experimental evidence reported in the literature. In this study, we provide definitive evidence of the ABC hydride generation mechanism, which shows that the generation of volatile hydrides occurs via formation of ABC intermediates between hydroboron species and the analyte substrate followed by the direct transfer of hydrogen from boron to the analyte atom, and fast hydrolysis leading to the final product.
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  • Analytical Chemistry 79, no. 7: 3008–3015.
LanguageEnglish
Peer reviewedYes
NRC numberNRC-INMS-4089
NPARC number8900184
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Record identifier4986e512-0abc-4d87-93ba-a939bf8bdf06
Record created2009-04-22
Record modified2020-05-10

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