Ozonolysis for the preparation of high oxidation-state transition-metal complexes and the crystal structure of [PPh4]2[Ru2O(µ-OCOEt)2Cl6]†

An ozone–oxygen mixture has been used to generate a number of high oxidation-state transition-metal complexes in aqueous solution at room temperature by simple and safe procedures. Species so prepared include the oxo species [OsVIIIO4], [RuVIIIO4], cis-[OsVIIIO4(OH)2]2–, trans-[OsVIO2(OH)4]2–, [RuVIIO4]–, trans-[RuVI(OH)2O3]2–, [VVO4]3– and the new complex [PPh4]2[Ru2O(µ-OCOEt)2Cl6] 1 for which the crystal structure is reported; the polyoxometalates K6[MnIVMo9O32]·10H2O, K8[MnIVW6O24]·6H2O, [NH4]2[MnIVMo6H6O24]·20H2O and Na8[CeIVW10O36]·8H2O; the chloro complexes [MIVCl6]2– (M = Pt, Pd, Ir) and [AuIIICl4]–, and manganic acetate [MnIII(OAc)3]·2H2O. Ozonolytic oxidation of coordinated benzylamine in cis-[RuII(bipy)2(NH2CH2Ph)2][PF6]2 to coordinated benzonitrile in cis-[RuII(bipy)2(NCPh)2][PF6]2 is also reported.