Air-Stable, Well-Soluble A(2)(I)[Nb6Cl18] Cluster Compounds (A(I) = Organic Cation): A New Route for Preparation, Single-Crystal Structures, Properties, and ESI-Mass Spectra

作者：Koenig Jonas; Dartsch Ina; Topp A; Guillamon Eva; Llusar Rosa^*; Koeckerling Martin

来源：Zeitschrift fur Anorganische und Allgemeine Chemie, 2016, 642(7): 572-578.

DOI：10.1002/zaac.201600039

• Cluster
• Niobium
• Dehydration
• Solubility
• ESI-MS

Five niobium cluster compounds of the A(2)(I)[Nb6Cl18] type (A(I) = organic cation: [nPr(4)N](+), [nBu(4)N](+), [BMIm](+), [Ph4P](+), and [PPN](+)) are obtained through treatment of [Nb6Cl14(H2O)(4)]center dot 4H(2)O with excess of thionyl chloride in the presence of an organic chloride, A(I)Cl. Single-crystal structure studies show that the compounds consist of discrete cations and cluster [Nb6Cl18](2-) anions. The cluster unit of the hydrated cluster starting material is oxidized by two electrons. Powder diffraction studies and NMR spectroscopic measurements show all compounds to crystallize without co-crystallized solvent molecules. They are air and water stable. The solubility in organic solvents changes to a great extent on changing the type of cation. The ESI-MS spectra of [nPr(4)N](2)[Nb6Cl18] and [Ph4P](2)[Nb6Cl18] show the pseudo-molecular peak of the anionic cluster as well as additional signals, which involve simultaneously chloride mass loss and reduction processes.

• 出版日期2016-4