Actinide Pnictinidene Chemistry: A Terminal Thorium Parent-Arsinidene Complex Stabilised by a Super-Bulky Triamidoamine Ligand
Actinide Pnictinidene Chemistry: A Terminal Thorium Parent-Arsinidene Complex Stabilised by a Super-Bulky Triamidoamine Ligand
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锕系磷亚胺化学：由超大型三酰氨基胺配体稳定的末端钍母体胂络合物
DOI：
10.1002/ange.202211627
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发表时间：
2022
影响因子：
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通讯作者：
Du J
中科院分区：
文献类型：
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作者：
Du J
我们报道了直接合成末端pnictidenes [An(TrenTCHS)(PnH)][M(2,2,2‐cryptand)] (TrenTCHS={N(CH2CH2NSiCy3)3}3−；An/Pn/M=Th/P/Na5, Th/As/K6, U/P/Na7, U/As/K8)及其转化为PnH2 [An(TrenTCHS)(PnH2)] （An/Pn=Th/P9, Th/As10, U/P11, U/As12）。使用超大体积的TrenTCHSligand对于获得完整的家族是必不可少的，并且6是一个前所未有的末端钍-砷化物配合物的例子，也是任何金属中第二个结构上经过验证的母体末端砷化物配合物。比较结构类似的[Th(TrenTIPS){μ‐As(H)K(15‐crown‐5)}]（TrenTIPS={N(CH2CH2NSiPri3)3}3−）中6的末端Th=AsH单元和桥接ThAs(H)K键，前者比后者具有更强的Th−As键，并且在去除静电结合的K离子后，Th=AsH键的性质总体上有很大的响应；σ -键变化不大，但π -键明显受到扰动。
We report the direct synthesis of the terminal pnictidenes [An(TrenTCHS)(PnH)][M(2,2,2‐cryptand)] (TrenTCHS={N(CH2CH2NSiCy3)3}3−; An/Pn/M=Th/P/Na5, Th/As/K6, U/P/Na7, U/As/K8) and their conversion to the pnictides [An(TrenTCHS)(PnH2)] (An/Pn=Th/P9, Th/As10, U/P11, U/As12). Use of the super‐bulky TrenTCHSligand was essential to accessing complete families, and6is an unprecedented example of a terminal thorium‐arsinidene complex and only the second structurally authenticated parent terminal arsinidene complex of any metal. Comparison of the terminal Th=AsH unit of6to the bridging ThAs(H)K linkage in structurally analogous [Th(TrenTIPS){μ‐As(H)K(15‐crown‐5)}] (TrenTIPS={N(CH2CH2NSiPri3)3}3−) reveals a stronger Th−As bond in the former compared to the latter, and a large response overall to the nature of the Th=AsH bonding upon removal of the electrostatically‐bound K‐ion; the σ‐bond changes little but the π‐bond is significantly perturbed.