In an attempt to produce a convenient starting material for the development of new interstitially centered, octahedral zirconium cluster compounds by solution-chemical methods, a new approach, using Na[Ph4B) to withdraw all six outer chlorides by precipitating them as NaCl, was explored. From a solution of K-2[(Zr6B)Cl-15] and Na[Ph4B] in acetonitrile, the tetraphenylborate salt ((Zr6B)CI12-(MeCN)(6)][Ph4B]center dot 1.6 MeCN (1) was obtained with high yield. It contains the [(Zr6B)CI12i(MeCN)(6)(a)](+) ion (2) with an octahedral metal core. The crystal structure of 1, which possesses high solubility in several organic solvents, is reported. Treatment of 1 with pyridine gave the new cluster phase [(Zr6B)CI12(Pyr(6)][Ph4B] center dot 2{(PyrH)[Ph4B]} (3), which was characterized as well by X-ray crystallography. An advantage of both title phases is that they contain Lewis acidic zirconium cluster units, which might be useful as catalysts, with the additional advantage of tuneable redox properties.