Studies on transition-metal nitrido and oxo complexes. Part 14. Carboxylato oxo-osmium(VI) and -ruthenium(VI) complexes and their reactions

Abstract

The new complexes [OsO₂(OCOR)Cl₂]^–[R = Me, Et or CH(Me)Et] and [RuO₂(OCOR)Cl₂]^–(R = Me, Et, Pr or CHF₂) have been prepared. In addition to functioning as catalytic oxidants for organic substrates in the presence of N-methylmorpholine N-oxide as co-oxidant, the acetato complexes [MO₂(OCOMe)Cl₂]^– in particular can be used as precursors for a wide variety of complexes. New species prepared from these include [OsO₂(NCO)₄]^2–, [OsO₂(SCN)₄]^2–, [OsO₂(acac)Cl₂]^–(acac = pentane-2,4-dionate), [Os(terpy)Cl₃]⁺(terpy = 2,2′ : 6′,2″-terpyridine), [OsO₂(S₂CNEt₂)₂] and [Ru(OH)(H₂O)(O₂COCR¹R²)Cl₂](R¹= R²= Me or Et; R¹= Me, R²= Et or Ph).