Sperlich Eric, Köckerling Martin
Universität Rostock, Institut für Chemie Anorganische Festkörperchemie, Albert-Einstein-Str. 3a, 18059, Rostock, Germany.
Present address: Universität Potsdam, Institut für Chemie, Karl-Liebknecht-Str. 24-25, 14476, Potsdam, Germany.
ChemistryOpen. 2021 Feb;10(2):248-254. doi: 10.1002/open.202000266. Epub 2021 Feb 3.
Four new hexanuclear niobium cluster compounds of the general formula Nb Cl (HIm) ⋅ x(solvent molecule) (HIm=1H-imidazole, A=mineral acid anion, Cl (n=2) (1), (SO ) (n=1) (2), (CrO ) (n=1) (3), and (HAsO ) (n=1) (4)) were prepared. Their synthesis can be done in basic ionic liquids, which form on the addition of a mineral acid, which also delivers the counter anion for the final cluster compound, to an excess of the 1H-imidazole. Some addition of an auxiliary solvent, like methanol, improves the speed of crystallisation. The cluster unit comprises a hexanuclear Nb unit of octahedral shape with the edges bridged by Cl atoms and the exo sites being occupied by N-bonded 1H-imidazole ligands. The cluster cation carries sixteen cluster-based electrons. Between the NH groups of the ligands of the cluster unit, the anions and the co-crystallised water (1), or 1H-imidazole and methanol molecules (2, 3, and 4) a network of hydrogen bonds exists.
制备了四种通式为Nb₆Cl₁₂(HIm)₆ₙ⋅x(溶剂分子)(HIm = 1H - 咪唑,A = 无机酸阴离子,Cl⁻(n = 2) (1)、(SO₄²⁻)(n = 1) (2)、(CrO₄²⁻)(n = 1) (3)和(HAsO₄²⁻)(n = 1) (4))的新型六核铌簇合物。它们的合成可以在碱性离子液体中进行,即在向过量的1H - 咪唑中加入无机酸(该无机酸也为最终的簇合物提供抗衡阴离子)时形成碱性离子液体。加入一些辅助溶剂,如甲醇,可提高结晶速度。簇单元由八面体形状的六核铌单元组成,其棱边由氯原子桥连,外部位点被N键合的1H - 咪唑配体占据。簇阳离子带有16个基于簇的电子。在簇单元配体的NH基团、阴离子和共结晶水(1)或1H - 咪唑与甲醇分子(2、3和4)之间存在氢键网络。