The reaction of Ar(3)GeBr (Ar = 2,6-(OtBu)(2)C(6)H(3)), which is the side product of the synthesis of the metalloid germanium cluster compound Ge(8)Ar(6), with the silver salt of the weakly coordinating anion (WCA) [Al(OR(f))(4)](-) (R(f) = C(CF(3))(3)) gives the free germyl cation Ar(3)Ge(+). Quantum chemical calculations open an insight into the bonding situation of this first free cation exhibiting aryl ligands and a first reaction leading to Ar(3)GeOH is presented.
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