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

Gardner, Benedict M.; Bal�zs, G�bor; Scheer, Manfred; Wooles, Ashley J.; Tuna, Floriana; McInnes, Eric J.L.; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Liddle, Stephen T.

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., McMaster, J., Lewis, W., Blake, A. 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: 1521-3773
• 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: https://nottingham-repository.worktribe.com/output/770039
• Publisher URL: https://doi.org/10.1002/anie.201508600
• Contract Date: Sep 27, 2017