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(Tren(TIPS))}(2)(mu-eta(2) :eta(2)-As2H2)] (3, ...
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(Tren(TIPS))}(2)(mu-eta(2) :eta(2)-As2H2)] (3, Tren(TIPS) = N(CH2CH2NSiPr3i)(3); Pr-i = 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 pi(*)-orbital. This experimentally confirms the theoretically predicted excellent p-acceptor character of HAsAsH, and is tantamount to full reduction to the diarsane-1,2- diide form.
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