Cluster Compounds with Oxidised, Hexanuclear [Nb(6)Cl(i) (12)I(a) (6)]( n−) Anions (n=2 or 3)

Four mixed‐halide cluster salts with chloride‐iodide‐supported octahedral Nb(6) metal atoms cores were prepared and investigated. The cluster anions have the formula [Nb(6)Cl(i) (12)I(a) (6)]( n−) with Cl occupying the inner ligand sites and I the outer one. They are one‐ or two‐electron‐oxidized (n=2 or 3) with respect to the starting material cluster. (Ph(4)P)(+) and (PPN)(+) function as counter cations. The X‐ray structures reveal a mixed occupation of the outer sites for only one compound, (PPN)(3)[Nb(6)Cl(i) (12)I(a) (5.047(9))Cl(a) (0.953)]. All four compounds are obtained in high yield. If in the chemical reactions a mixture of acetic anhydride, CH(2)Cl(2), and trimethylsilyl iodide is used, the resulting acidic conditions lead to form the two‐electron‐oxidised species (n=2) with 14 cluster‐based electrons (CBEs). If only acetic anhydride is used, the 15 CBE species (n=3) is obtained in high yield. Interesting intermolecular bonding is found in (Ph(4)P)(2)[Nb(6)Cl(i) (12)I(a) (6)] ⋅ 4CH(2)Cl(2) with I⋅⋅⋅I halogen bonding and π‐π bonding interactions between the phenyl rings of the cations in (PPN)(3)[Nb(6)Cl(i) (12)I(a) (5.047(9))Cl(a) (0.953)]. The solubility of (Ph(4)P)(2)[Nb(6)Cl(i) (12)I(a) (6)] ⋅ 4CH(2)Cl(2) has been determined qualitatively in a variety of solvents, and good solubility in the aprotic solvents CH(3)CN, THF and CH(2)Cl(2) has been found.