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

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

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 authentica...

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Bibliographic Details
Main Authors: 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.
Format: Article
Published: Wiley-VCH Verlag 2015
Subjects:
arsenic; back-bonding; density functional theory; diarsene; uranium
Online Access:https://eprints.nottingham.ac.uk/46637/
Description
Summary: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.

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