Dioxoruthenium Porphyrins Research Articles

ChemInform Abstract: Resonance Raman Spectra of Reaction Intermediates in the Oxidation Process of Ruthenium(II) and Iron(II) Porphyrins

The dioxo ruthenium porphyrins, RuP(O){sub 2} (P = TPP and TMP), were prepared by the oxidation of RuP(CO) with m-chloroperoxybenzoic acid (m-CPBA). The resonance Raman and IR spectra of RuP(O){sub 2} were measured and their O{double bond}Ru{double bond}O vibrations including the {sup 16}O{double bond}Ru{double bond}{sup 18}O and {sup 18}O{double bond}Ru{double bond}{sup 18}O analogues assigned by normal coordinate calculations. A reaction scheme involving two successive O-O bond cleavages of m-CPBA was proposed based on the observed intensity patterns of the O{double bond}Ru{double bond}O vibrations. In all cases, the peroxo-bridged species and the ferryl species are present at low temperature, and the former is converted into the latter by raising the temperature.

Resonance Raman spectra of reaction intermediates in oxidation process of ruthenium(II) and iron(II) porphyrins

The dioxo ruthenium porphyrins, RuP(O){sub 2} (P = TPP and TMP), were prepared by the oxidation of RuP(CO) with m-chloroperoxybenzoic acid (m-CPBA). The resonance Raman and IR spectra of RuP(O){sub 2} were measured and their O{double bond}Ru{double bond}O vibrations including the {sup 16}O{double bond}Ru{double bond}{sup 18}O and {sup 18}O{double bond}Ru{double bond}{sup 18}O analogues assigned by normal coordinate calculations. A reaction scheme involving two successive O-O bond cleavages of m-CPBA was proposed based on the observed intensity patterns of the O{double bond}Ru{double bond}O vibrations. In all cases, the peroxo-bridged species and the ferryl species are present at low temperature, and the former is converted into the latter by raising the temperature.