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Condensation cascades and methylgroup transfer reactions during the formation of arsane, methyl- and dimethylarsane by aqueous borohydride and (methyl) arsenates

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Abstract

The formation of volatile products during the reaction of As(iii), As(v), MeAsO(OH)2, and Me2AsO(OH) with aqueous NaBH4 has been investigated, and the formation of arsanes, diarsanes, and triarsanes has been detected. The presence of triarsanes is reported here for the first time. Diarsanes and triarsanes are likely formed in condensation cascade reactions, whereas trimethylarsane arises via the transfer of a methyl group. The formation of volatile by-products is considerably reduced by increasing the acidity of the medium and the concentration of NaBH4 or by the addition of thiols, such as cysteine. A reaction scheme is proposed which reconciles the evidence reported herein and elsewhere in the literature that is valid for both analytical (trace analysis) and non-analytical reaction conditions.

Condensation cascade and methyl transfer reactions taking place during the hydride generation of As-compounds under non-analytical conditions. They are originated by the interaction of As reaction intermdiates, among them, and with the other As species containing As-H and As-OH bonds.

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Authors and Affiliations

  1. CNR, Consiglio Nazionale delle Ricerche, Istituto di Chimica dei Composti Organometallici, Via G. Moruzzi, 1, 56124, Pisa, Italy

    Alessandro D’Ulivo

  2. Institute for National Measurement Standards, National Research Council Canada, Ottawa, ON, K1A 0R6, Canada

    Juris Meija, Zoltán Mester & Ralph E. Sturgeon

  3. Scuola Normale Superiore, Piazza dei Cavalieri, 7, 56126, Pisa, Italy

    Enea Pagliano

Authors
  1. Alessandro D’Ulivo
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  2. Juris Meija
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  3. Zoltán Mester
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  4. Enea Pagliano
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  5. Ralph E. Sturgeon
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Correspondence to Alessandro D’Ulivo.

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D’Ulivo, A., Meija, J., Mester, Z. et al. Condensation cascades and methylgroup transfer reactions during the formation of arsane, methyl- and dimethylarsane by aqueous borohydride and (methyl) arsenates. Anal Bioanal Chem 402, 921–933 (2012). https://doi.org/10.1007/s00216-011-5503-4

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  • DOI: https://doi.org/10.1007/s00216-011-5503-4

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