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Isolation of Elusive HAsAsH in a Crystalline Diuranium(IV) Complex
Author(s) -
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.
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201508600
Subject(s) - deprotonation , uranium , molecule , electrochemistry , crystallography , chemistry , acceptor , phase (matter) , characterization (materials science) , materials science , nanotechnology , organic chemistry , ion , physics , electrode , metallurgy , condensed matter physics
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(Tren TIPS )} 2 (μ‐η 2 :η 2 ‐As 2 H 2 )] ( 3 , Tren TIPS =N(CH 2 CH 2 NS i Pr i 3 ) 3 ; Pr i =CH(CH 3 ) 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.