Niobium Alcoholate Clusters with an Octahedral Arrangement of Metal Atoms: [K(CH3OH)4]2 [Nb6(OCH3)18] and [Na([18]crown‐6)(C2H5OH)2]2 [Nb6(OC2H5)12(NCS)6]
Complete exchange : [M6X12] type cluster compounds with an octahedral M6 metal atom arrangement, which is completely surrounded by alcoholato ligands, were unknown until now. The first representatives are prepared containing a [Nb6(OR)12]4+ unit (R=CH3 or C2H5). They are accessible at elevated temperatures from strongly basic alcoholate solutions of [Nb6Cl12]2+‐containing precursors. C gray, H white, K turquoise, Nb blue, O red.