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Octahedral clusters of the [M 6 X 12 ] type offer numerous possibilities to form structural arrangements through different choices of bonding situations. In this paper a series of new cluster compounds of the transition metal niobium is described, which consist of the [Nb 6 Cl 18 ] 2-, and in one case [Nb 6 Cl 18 ] 3-, anion and protonated N-base cations ([MIm-H] + , [nPr 3 N-H] + , [TMGu-H] + , and [Tzn-H] +). They all are prepared using water scavenger compounds [SOCl 2 or (Ac) 2 O] under oxidising conditions, resulting in two-electron (or one-electron, respectively) oxidized cluster units with respect to the starting material [Nb 6 Cl 14 (H 2 O) 4 ]•4H 2 O. Of five members of this group single-crystal

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