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Gardner BM, Balázs G, Scheer M, et al. Isolation of Elusive HAsAsH in a Crystalline Diuranium(IV) Complex. Angew Chem Int Ed Engl. 2015;54(50):15250-4doi: 10.1002/anie.201508600.
Gardner, B. M., Balázs, G., Scheer, M., Wooles, A. J., Tuna, F., McInnes, E. J., McMaster, J., Lewis, W., Blake, A. J., & Liddle, S. T. (2015). Isolation of Elusive HAsAsH in a Crystalline Diuranium(IV) Complex. Angewandte Chemie (International ed. in English), 54(50), 15250-4. https://doi.org/10.1002/anie.201508600
Gardner, Benedict M, et al. "Isolation of Elusive HAsAsH in a Crystalline Diuranium(IV) Complex." Angewandte Chemie (International ed. in English) vol. 54,50 (2015): 15250-4. doi: https://doi.org/10.1002/anie.201508600
Gardner BM, Balázs G, Scheer M, Wooles AJ, Tuna F, McInnes EJ, McMaster J, Lewis W, Blake AJ, Liddle ST. Isolation of Elusive HAsAsH in a Crystalline Diuranium(IV) Complex. Angew Chem Int Ed Engl. 2015 Dec 07;54(50):15250-4. doi: 10.1002/anie.201508600. Epub 2015 Oct 28. PMID: 26510123; PMCID: PMC4691330.
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Angew Chem Int Ed Engl. 2015 Dec 07;54(50):15250-4. doi: 10.1002/anie.201508600. Epub 2015 Oct 28.

Isolation of Elusive HAsAsH in a Crystalline Diuranium(IV) Complex.

Angewandte Chemie (International ed. in English)

Benedict M Gardner, Gábor Balázs, Manfred Scheer, Ashley J Wooles, Floriana Tuna, Eric J L McInnes, Jonathan McMaster, William Lewis, Alexander J Blake, Stephen T Liddle

Affiliations

  1. School of Chemistry, University of Manchester, Oxford Road, Manchester, M13 9PL (UK).
  2. Institut of Inorganic Chemistry, University of Regensburg, Universitätsstrasse 31, 93053 Regensburg (Germany).
  3. Institut of Inorganic Chemistry, University of Regensburg, Universitätsstrasse 31, 93053 Regensburg (Germany). [email protected].
  4. School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD (UK).
  5. School of Chemistry, University of Manchester, Oxford Road, Manchester, M13 9PL (UK). [email protected].

PMID: 26510123 PMCID: PMC4691330 DOI: 10.1002/anie.201508600

Abstract

The HAsAsH molecule has hitherto only been proposed tentatively as a short-lived species generated in electrochemical or microwave-plasma experiments. After two centuries of inconclusive or disproven claims of HAsAsH formation in the condensed phase, we report the isolation and structural authentication of HAsAsH in the diuranium(IV) complex [{U(Tren(TIPS) )}2 (μ-η(2) :η(2) -As2 H2 )] (3, Tren(TIPS) =N(CH2 CH2 NSiPr(i) 3 )3 ; Pr(i) =CH(CH3 )2 ). Complex 3 was prepared by deprotonation and oxidative homocoupling of an arsenide precursor. Characterization and computational data are consistent with back-bonding-type interactions from uranium to the HAsAsH π*-orbital. This experimentally confirms the theoretically predicted excellent π-acceptor character of HAsAsH, and is tantamount to full reduction to the diarsane-1,2-diide form.

© 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

Keywords: arsenic; back-bonding; density functional theory; diarsene; uranium

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