title: Isolation of Elusive HAsAsH in a Crystalline Diuranium(IV) Complex.
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). Complex3was 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.
authors.affiliation: School of Chemistry, University of Manchester, Oxford Road, Manchester, M13 9PL (UK).
authors.forename: Benedict M
authors.initials: BM
authors.lastname: Gardner
authors.affiliation: Institut of Inorganic Chemistry, University of Regensburg, Universitätsstrasse 31, 93053 Regensburg (Germany).
authors.forename: Gábor
authors.initials: G
authors.lastname: Balázs
authors.affiliation: Institut of Inorganic Chemistry, University of Regensburg, Universitätsstrasse 31, 93053 Regensburg (Germany).
authors.forename: Manfred
authors.initials: M
authors.lastname: Scheer
authors.affiliation: School of Chemistry, University of Manchester, Oxford Road, Manchester, M13 9PL (UK).
authors.forename: Ashley J
authors.initials: AJ
authors.lastname: Wooles
authors.affiliation: School of Chemistry, University of Manchester, Oxford Road, Manchester, M13 9PL (UK).
authors.forename: Floriana
authors.initials: F
authors.lastname: Tuna
authors.affiliation: School of Chemistry, University of Manchester, Oxford Road, Manchester, M13 9PL (UK).
authors.forename: Eric J L
authors.initials: EJ
authors.lastname: McInnes
authors.affiliation: School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD (UK).
authors.forename: Jonathan
authors.initials: J
authors.lastname: McMaster
authors.affiliation: School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD (UK).
authors.forename: William
authors.initials: W
authors.lastname: Lewis
authors.affiliation: School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD (UK).
authors.forename: Alexander J
authors.initials: AJ
authors.lastname: Blake
authors.affiliation: School of Chemistry, University of Manchester, Oxford Road, Manchester, M13 9PL (UK).
authors.forename: Stephen T
authors.initials: ST
authors.lastname: Liddle
keywords: Arsen; Diarsen; Dichtefunktionalrechnungen; Rückbindung; Uran