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

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

Authors

Benedict M. Gardner

Gábor Balázs

Manfred Scheer

Ashley J. Wooles

Floriana Tuna

Eric J.L. McInnes

William Lewis

Alexander J. Blake

Stephen T. Liddle



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(TrenTIPS)}2(μ-η2:η2-As2H2)] (3, TrenTIPS=N(CH2CH2NSiPri3)3; Pri=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.

Citation

Gardner, B. M., Balázs, G., Scheer, M., Wooles, A. J., Tuna, F., McInnes, E. J., …Liddle, S. T. (2015). Isolation of Elusive HAsAsH in a Crystalline Diuranium(IV) Complex. Angewandte Chemie International Edition, 54(50), 15250-15254. https://doi.org/10.1002/anie.201508600

Journal Article Type Article
Acceptance Date Sep 14, 2015
Online Publication Date Oct 28, 2015
Publication Date Dec 7, 2015
Deposit Date Sep 27, 2017
Publicly Available Date Sep 27, 2017
Journal Angewandte Chemie International Edition
Print ISSN 1433-7851
Electronic ISSN 1433-7851
Publisher Wiley
Peer Reviewed Peer Reviewed
Volume 54
Issue 50
Pages 15250-15254
DOI https://doi.org/10.1002/anie.201508600
Keywords arsenic; back-bonding; density functional theory; diarsene; uranium
Public URL http://eprints.nottingham.ac.uk/id/eprint/46637
Publisher URL https://doi.org/10.1002/anie.201508600
Copyright Statement Copyright information regarding this work can be found at the following address: http://creativecommons.org/licenses/by/4.0

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Copyright Statement
Copyright information regarding this work can be found at the following address: http://creativecommons.org/licenses/by/4.0





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