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Strong Cluster-Supported Brønsted Acids: Hexanuclear Niobium Cluster Compounds with Protonated Crown Ether Cations: (Crown-H)2[Nb6Cl12iX6a] (X = Cl or Br) and the Intermediate [Nb6Cl16(H2O)2]·4 dioxane
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2022-09-28 , DOI: 10.1021/acs.inorgchem.2c02279 Jonas König 1 , Torsten Gutmann 2 , Gerd Buntkowsky 2 , Martin Köckerling 1, 3
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2022-09-28 , DOI: 10.1021/acs.inorgchem.2c02279 Jonas König 1 , Torsten Gutmann 2 , Gerd Buntkowsky 2 , Martin Köckerling 1, 3
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Six cluster salts which consist of hexanuclear cluster anions [Nb6Cl12iX6a]2– (X = Cl or Br) and protonated crown ether molecules (15-crown-5 (15cr5) and 12-crown-4 (12cr4)) or crown ether-stabilized oxonium cations as well as one compound consisting of neutral cluster units, [Nb6Cl16(H2O)2]·4 dioxane, were synthesized in good to high yields. The single-crystal X-ray structures of six of these compounds were determined. The cation/anion ratios and the bond distances confirm in all cases oxidized cluster cores with 14 cluster-based electrons. The cations of the cluster salts are either sandwich-type dimers of the formula [(15cr5)H]22+ or [(15cr5)(H3O)]22+ with the protons or oxonium ions embedded in between the crown ether rings or monomeric units in the case of [(12cr4)H]+. 1H NMR investigations show that the cluster salts are strong Brønsted acids. The fact that the cluster core of [Nb6Cl16(H2O)2]·4 dioxane is oxidized but still carries water ligands indicates that within the multi-step reaction sequence of the formation of the cluster-supported acids, the oxidation step happens much faster than the ligand exchange steps. Temperature-dependent 2H MAS NMR spectra of deuterium-exchanged [(15cr5)H]2[Nb6Cl18]·2 CHCl3 are indicative of dynamic processes of the hydrogen-bonded protons within the crown ether molecule.
中文翻译：
强簇支持的布朗斯台德酸：具有质子化冠醚阳离子的六核铌簇化合物：(Crown-H)2[Nb6Cl12iX6a] (X = Cl 或 Br) 和中间体 [Nb6Cl16(H2O)2]·4 二恶烷
由六核簇阴离子 [Nb 6 Cl 12 i X 6 a ] 2- ( X = Cl 或 Br) 和质子化冠醚分子 (15-crown-5 (15cr5) 和 12-crown-4 (12cr4 )) 或冠醚稳定的氧鎓阳离子以及一种由中性簇单元组成的化合物，[Nb 6 Cl 16 (H 2 O) 2]·4 二恶烷，以良好至高产率合成。确定了其中六种化合物的单晶 X 射线结构。阳离子/阴离子比和键距在所有情况下都证实了具有 14 个基于簇的电子的氧化簇核。簇盐的阳离子是夹心型二聚体，分子式为 [(15cr5)H] 2 2+或 [(15cr5)(H 3 O)] 2 2+，质子或氧鎓离子嵌入冠醚之间[(12cr4)H] +的情况下的环或单体单元。1 H NMR 研究表明簇盐是强布朗斯台德酸。[Nb 6 Cl 16 (H 2O) 2 ]·4 二恶烷被氧化但仍带有水配体表明在形成簇负载酸的多步反应序列中，氧化步骤发生得比配体交换步骤快得多。氘交换的[(15cr5)H] 2 [Nb 6 Cl 18 ]·2 CHCl 3的温度依赖性2 H MAS NMR光谱表明冠醚分子内氢键质子的动态过程。
更新日期：2022-09-28
中文翻译：
强簇支持的布朗斯台德酸：具有质子化冠醚阳离子的六核铌簇化合物：(Crown-H)2[Nb6Cl12iX6a] (X = Cl 或 Br) 和中间体 [Nb6Cl16(H2O)2]·4 二恶烷
由六核簇阴离子 [Nb 6 Cl 12 i X 6 a ] 2- ( X = Cl 或 Br) 和质子化冠醚分子 (15-crown-5 (15cr5) 和 12-crown-4 (12cr4 )) 或冠醚稳定的氧鎓阳离子以及一种由中性簇单元组成的化合物，[Nb 6 Cl 16 (H 2 O) 2]·4 二恶烷，以良好至高产率合成。确定了其中六种化合物的单晶 X 射线结构。阳离子/阴离子比和键距在所有情况下都证实了具有 14 个基于簇的电子的氧化簇核。簇盐的阳离子是夹心型二聚体，分子式为 [(15cr5)H] 2 2+或 [(15cr5)(H 3 O)] 2 2+，质子或氧鎓离子嵌入冠醚之间[(12cr4)H] +的情况下的环或单体单元。1 H NMR 研究表明簇盐是强布朗斯台德酸。[Nb 6 Cl 16 (H 2O) 2 ]·4 二恶烷被氧化但仍带有水配体表明在形成簇负载酸的多步反应序列中，氧化步骤发生得比配体交换步骤快得多。氘交换的[(15cr5)H] 2 [Nb 6 Cl 18 ]·2 CHCl 3的温度依赖性2 H MAS NMR光谱表明冠醚分子内氢键质子的动态过程。
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