Isolation of elusive HAsAsH in a crystalline diuranium(IV) complex

Gardner, Benedict M. and Balázs, Gábor and Scheer, Manfred and Wooles, Ashley J. and Tuna, Floriana and McInnes, Eric J.L. and McMaster, Jonathan and Lewis, William and Blake, Alexander J. and Liddle, Stephen T. (2015) Isolation of elusive HAsAsH in a crystalline diuranium(IV) complex. Angewandte Chemie International Edition, 54 (50). pp. 15250-15254. ISSN 1433-7851

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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.

Item Type: Article
Keywords: arsenic; back-bonding; density functional theory; diarsene; uranium
Schools/Departments: University of Nottingham, UK > Faculty of Science > School of Chemistry
Identification Number: 10.1002/anie.201508600
Depositing User: Lewis, William
Date Deposited: 27 Sep 2017 13:57
Last Modified: 14 Oct 2017 08:31
URI: http://eprints.nottingham.ac.uk/id/eprint/46637

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