High-Valent Ruthenium(IV) and -(VI) Oxo Complexes of Octaethylporphyrin. Synthesis, Spectroscopy, and Reactivities

Article abstract of DOI:10.1021/ja00206a007

Oxidation of by m-chloroperoxybenzoic acid in methanol gave , isolated as air-stable diamagnetic purple solid (μ_eff ca. 0 μ_B). shows one intense IR band at 821 cm^-1 assignable to ν_as (O=Ru=O) stretch.In CH2Cl2, it reacts with olefins to give epoxides and 2O in quantitative yields.In alcohols (ROH), the epoxidation reactions give , which readily dimerizes to 2O in noncoordinating solvents. is paramagneticwith measured μ_eff of 3.1 μ_B.Its (1)H NMR spectrum shows three broad singlets, the paramagnetic isotropic shifts of which vary inversely with temperature.The E⁰ for the /^- couple in CH2Cl2/py (py = pyridine) is -0.86 V vs Cp2Fe^+/0.In CH2Cl2/py solution, reacts with olefins to give and epoxides.