Du Jingzhen, Dollberg Kevin, Seed John A, Wooles Ashley J, von Hänisch Carsten, Liddle Stephen T
Department of Chemistry and Centre for Radiochemistry Research, The University of Manchester, Oxford Road, Manchester, M13 9PL, United Kingdom.
Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35043 Marburg, Germany.
Inorg Chem. 2024 Oct 28;63(43):20153-20160. doi: 10.1021/acs.inorgchem.4c00923. Epub 2024 May 20.
Reaction of the cesium antimonide complex [Cs(18C6)][SbH] (, 18C6 = 18-crown-6 ether) with the triamidoamine actinide separated ion pairs [An(Tren)(L)][BPh] (Tren = {N(CHCHNSiPr)}; An/L = Th/DME (); U/THF ()) affords the triactinide undeca-antimontriide Zintl clusters [{An(Tren)}(μ-Sb)] (An = Th (), U ()) by dehydrocoupling. Clusters and provide two new examples of the Sb Zintl trianion and are unprecedented examples of molecular Sb being coordinated to anything since all previous reports featured isolated Sb Zintl trianions in separated ion quadruple formulations with noncoordinating cations. Quantum chemical calculations describe dominant ionic An-Sb interactions in and , though the data suggest that the latter exhibits slightly more covalent An-Sb linkages than the former. Complexes and have been characterized by single crystal X-ray diffraction, NMR, IR, and UV/vis/NIR spectroscopies, elemental analysis, and quantum chemical calculations.
铯锑配合物[Cs(18C6)][SbH]（18C6 = 18-冠-6醚）与三酰胺基胺锕系元素分离离子对[An(Tren)(L)][BPh]（Tren = {N(CHCHNSiPr)}；An/L = Th/DME（）；U/THF（））反应，通过脱氢偶联生成三锕系十一锑化物Zintl簇[{An(Tren)}(μ-Sb)]（An = Th（），U（））。簇合物 和 提供了Sb Zintl三阴离子的两个新例子，并且是分子态Sb与其他物质配位的前所未有的例子，因为之前所有的报道都以分离离子四重态形式存在孤立的Sb Zintl三阴离子与非配位阳离子。量子化学计算描述了簇合物 和 中主要的离子型An-Sb相互作用，尽管数据表明后者的An-Sb键比前者略显共价性。配合物 和 已通过单晶X射线衍射、核磁共振、红外光谱、紫外/可见/近红外光谱、元素分析和量子化学计算进行了表征。
