Institut für Anorganische Chemie, Christian-Albrechts-Universität zu Kiel, 24118, Kiel, Germany.
Institut für Anorganische Chemie, RWTH Aachen University, 52074, Aachen, Germany.
Angew Chem Int Ed Engl. 2018 Mar 5;57(11):2972-2975. doi: 10.1002/anie.201712417. Epub 2018 Feb 12.
A water-soluble derivative of the polyoxovanadate {V E O } (E=semimetal) archetype enables the study of cluster shell rearrangements driven by supramolecular interactions. A reaction unique to E=Sb, induced exclusively by ligand metathesis in peripheral [Ni(ethylenediamine) ] counterions, results in the formation of the metastable α * configurational isomer of the {V Sb O } cluster type. Contrary to all other polyoxovanadate shell architectures, this isomer comprises an inward-oriented vanadyl group and is ca. 50 and 12 kJ mol higher in energy than the previously isolated α and β isomers, respectively. We discuss this unexpected reaction in light of supramolecular Sb-O⋅⋅⋅V and Sb-O⋅⋅⋅Sb contacts manifested in {V Sb O } dimers detected in the solid state. ESI MS experiments confirm the stability of these dimers also in solution and in the gas phase. DFT calculations indicate that other, as of yet elusive isomers of {V Sb }, might be accessible as well.
一种多钒酸盐{V E O}（E=类金属）原型的水溶性衍生物能够研究由超分子相互作用驱动的簇壳重排。E=Sb 的反应是独特的，仅由外围[Ni(乙二胺)]抗衡离子的配体交换诱导，导致形成亚稳的{V Sb O} 簇型的α*构型异构体。与所有其他多钒酸盐壳层结构不同，这种异构体包含一个向内取向的钒氧基，其能量分别比之前分离的α和β异构体高约 50 和 12kJ/mol。我们根据在固态中检测到的{V Sb O} 二聚体中表现出的 Sb-O⋅⋅⋅V 和 Sb-O⋅⋅⋅Sb 超分子接触，讨论了这种出乎意料的反应。ESI MS 实验证实这些二聚体在溶液中和气相中也稳定存在。DFT 计算表明，其他尚未被发现的{V Sb}异构体也可能是可接近的。
