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

Abstract

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 [Os^VIIIO₄], [Ru^VIIIO₄], cis-[Os^VIIIO₄(OH)₂]^2–, trans-[Os^VIO₂(OH)₄]^2–, [Ru^VIIO₄]^–, trans-[Ru^VI(OH)₂O₃]^2–, [V^VO₄]^3– and the new complex [PPh₄]₂[Ru₂O(µ-OCOEt)₂Cl₆] 1 for which the crystal structure is reported; the polyoxometalates K₆[Mn^IVMo₉O₃₂]·10H₂O, K₈[Mn^IVW₆O₂₄]·6H₂O, [NH₄]₂[Mn^IVMo₆H₆O₂₄]·20H₂O and Na₈[Ce^IVW₁₀O₃₆]·8H₂O; the chloro complexes [M^IVCl₆]^2– (M = Pt, Pd, Ir) and [Au^IIICl₄]^–, and manganic acetate [Mn^III(OAc)₃]·2H₂O. Ozonolytic oxidation of coordinated benzylamine in cis-[Ru^II(bipy)₂(NH₂CH₂Ph)₂][PF₆]₂ to coordinated benzonitrile in cis-[Ru^II(bipy)₂(NCPh)₂][PF₆]₂ is also reported.