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f-Element Zintl Chemistry: Actinide-Mediated Dehydrocoupling of H 2 Sb 1- Affords the Trithorium and Triuranium Undeca-Antimontriide Zintl Clusters [{An(Tren TIPS )} 3 (μ 3 -Sb 11 )] (An = Th, U; Tren TIPS = {N(CH 2 CH 2 NSi i Pr 3 ) 3 } 3- ).

Jingzhen DuKevin DollbergJohn A SeedAshley J WoolesCarsten von HänischStephen T Liddle
Published in: Inorganic chemistry (2024)
Reaction of the cesium antimonide complex [Cs(18C6) 2 ][SbH 2 ] ( 1 , 18C6 = 18-crown-6 ether) with the triamidoamine actinide separated ion pairs [An(Tren TIPS )(L)][BPh 4 ] (Tren TIPS = {N(CH 2 CH 2 NSi i Pr 3 ) 3 } 3- ; An/L = Th/DME ( 2Th ); U/THF ( 2U )) affords the triactinide undeca-antimontriide Zintl clusters [{An(Tren TIPS )} 3 (μ 3 -Sb 11 )] (An = Th ( 3Th ), U ( 3U )) by dehydrocoupling. Clusters 3Th and 3U provide two new examples of the Sb 11 3- Zintl trianion and are unprecedented examples of molecular Sb 11 3- being coordinated to anything since all previous reports featured isolated Sb 11 3- Zintl trianions in separated ion quadruple formulations with noncoordinating cations. Quantum chemical calculations describe dominant ionic An-Sb interactions in 3Th and 3U , though the data suggest that the latter exhibits slightly more covalent An-Sb linkages than the former. Complexes 3Th and 3U have been characterized by single crystal X-ray diffraction, NMR, IR, and UV/vis/NIR spectroscopies, elemental analysis, and quantum chemical calculations.
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