New Hexanuclear Niobium Cluster Compounds with Pyridine and N-Methylpyrrolidone Ligands: [Nb6Cl12(Pyr)6][AlCl4]2 and [Nb6Cl12(NMP)6][GaCl4]2

The study is focused on the preparation, characterization, and structure elucidation of two new molecular cluster complexes of niobium, one with an aromatic N donor ligand, the other one with an O‐carboxamide ligand: [Nb6Cl12(Pyr)6][AlCl4]2 (1) (Pyr = pyridine) and [Nb6Cl12(NMP)6][GaCl4]2 (2) (NMP = N‐methyl‐pyrrolidone). The synthesis of such substituted niobium cluster compounds, starting from easily accessible A4I[Nb6Cl18] (AI = alkali metal cation) materials is best done using a two‐step protocol. First the solid state precursor is heated together with acetonitrile and in the second step the ligand exchange is performed. The molecular structures of 1 and 2 in the solid state were determined by single‐crystal X‐ray diffraction. The infrared spectrum of 1 was recorded as well.