Isolation of Elusive HAsAsH in a Crystalline Diuranium(IV) Complex.
Isolation of Elusive HAsAsH in a Crystalline Diuranium(IV) Complex.
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DOI：
10.1002/anie.201508600
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发表时间：
2015-12-07
期刊：
影响因子：
--
通讯作者：
Liddle ST
中科院分区：
文献类型：
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作者：
Gardner BM;Balázs G;Scheer M;Wooles AJ;Tuna F;McInnes EJ;McMaster J;Lewis W;Blake AJ;Liddle ST
迄今为止，HAsAsH分子仅被暂时提出作为在电化学或微波等离子体实验中产生的短寿命物种。经过两个世纪的不确定性或被证明的HAsAsH形成在凝聚相的索赔，我们报告的分离和结构认证的HAsAsH在铀（IV）配合物[{U（TrenTIPS）}2（μ-η2：η2-As 2 H2）]（3，TrenTIPS=N（CH 2CH 2NSiPri 3）3; Pri=CH（CH 3）2）。配合物3是通过砷化物前体的去质子化和氧化偶联制备的。表征和计算数据与从铀到HAsAsH π*-轨道的背键型相互作用一致。这在实验上证实了理论预测的HAsAsH优良的π受体特征，并且相当于完全还原为二砷烷-1，2-二化物形式。
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.