Isolation of Elusive HAsAsH in a Crystalline Diuranium(IV) Complex |
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| Authors: | Dr Benedict M Gardner Dr Gábor Balázs Prof?Dr Manfred Scheer Dr Ashley J Wooles Dr Floriana Tuna Prof Eric J L McInnes Dr Jonathan McMaster Dr William Lewis Prof?Dr Alexander J Blake Prof?Dr Stephen T Liddle |
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| Institution: | 1. School of Chemistry, University of Manchester, Oxford Road, Manchester, M13 9PL (UK);2. Institut of Inorganic Chemistry, University of Regensburg, Universit?tsstrasse 31, 93053 Regensburg (Germany);3. School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD (UK) |
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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. |
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| Keywords: | arsenic back‐bonding density functional theory diarsene uranium |
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