锕系元素磷族元素亚烷基化学：一种由超庞大的三酰胺胺配体稳定的末端钍母体-亚砷基配合物。
Actinide Pnictinidene Chemistry: A Terminal Thorium Parent-Arsinidene Complex Stabilised by a Super-Bulky Triamidoamine Ligand.
作者信息
Du Jingzhen, Balázs Gábor, Seed John A, Cryer Jonathan D, Wooles Ashley J, Scheer Manfred, Liddle Stephen T
机构信息
Department of Chemistry, The University of Manchester, Oxford Road, Manchester, M13 9PL, UK.
Institute of Inorganic Chemistry, University of Regensburg, Universitätsstr. 31, 93053, Regensburg, Germany.
出版信息
Angew Chem Int Ed Engl. 2022 Dec 12;61(50):e202211627. doi: 10.1002/anie.202211627. Epub 2022 Nov 16.
We report the direct synthesis of the terminal pnictidenes [An(Tren )(PnH)][M(2,2,2-cryptand)] (Tren ={N(CH CH NSiCy ) } ; An/Pn/M=Th/P/Na 5, Th/As/K 6, U/P/Na 7, U/As/K 8) and their conversion to the pnictides [An(Tren )(PnH )] (An/Pn=Th/P 9, Th/As 10, U/P 11, U/As 12). Use of the super-bulky Tren ligand was essential to accessing complete families, and 6 is 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 of 6 to the bridging ThAs(H)K linkage in structurally analogous [Th(Tren ){μ-As(H)K(15-crown-5)}] (Tren ={N(CH CH NSiPr ) } ) 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.
我们报道了末端磷族元素烯[An(Tren)(PnH)][M(2,2,2-穴醚)]（Tren ={N(CH₂CH₂NSiCy₃)₃}；An/Pn/M = Th/P/Na 5、Th/As/K 6、U/P/Na 7、U/As/K 8）的直接合成及其向磷族化物[An(Tren)(Pn)]（An/Pn = Th/P 9、Th/As 10、U/P 11、U/As 12）的转化。使用超大位阻的Tren配体对于获得完整的系列化合物至关重要，并且6是末端钍-亚砷烯配合物的一个前所未有的例子，也是任何金属的第二个经结构验证的母体末端亚砷烯配合物。将6的末端Th=AsH单元与结构类似的[Th(Tren){μ-As(H)K(15-冠醚-5)}]（Tren ={N(CH₂CH₂NSiPr₃)₃}）中的桥连ThAs(H)K键进行比较，结果表明前者中的Th-As键比后者更强，并且在去除静电结合的K离子后，总体上对Th=AsH键的性质有很大的响应；σ键变化不大，但π键受到显著扰动。
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