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• W1998088247 endingPage "4685" @default.
• W1998088247 startingPage "4680" @default.
• W1998088247 abstract "Resonance Raman spectra are reported for the iron complex of tetramethyltetramesitylporphine (TMTMP) in its ferric, ferryl, and ferryl π-cation forms. For comparison, the spectra of the copper complex and its corresponding π-cation radical are included. Vibrational assignments have been made based on depolarization ratio measurements and isotopic frequency shifts associated with methine deuteration. The observed behavior of the ν2 and ν11 RR “marker bands”, which shift to higher frequency upon oxidation of the macrocycle, is consistent with previously reported NMR studies wherein these radicals were shown to have predominately 2A1u ground states. The ν(Fe−O) stretching modes of the ferryl species (both five- and six-coordinate) and (OFeTMTMP•+)(ClO4-) are identified by their 16O/18O isotope shifts. This is the first observation of the ν(Fe−O) mode for a 2A1u type ferryl π-cation radical. Its frequency (833 cm-1) is virtually identical with that of the corresponding derivative of meso-tetramesitylporphyrin (TMP), (OFeTMP+)(ClO4-), a 2A2u radical, which exhibits its ν(Fe−O) mode at 835 cm-1. These data imply that the ν(Fe−O) modes of ferrylporphyrin π-cation radicals are rather insensitive to radical type (2A1u vs 2A2u)behavior which is surprisingly different from the previously observed sensitivity of the ν(V−O) modes of corresponding vanadylporphyrin π-cation radicals." @default.
• W1998088247 created "2016-06-24" @default.
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• W1998088247 date "1996-01-01" @default.
• W1998088247 modified "2023-09-24" @default.
• W1998088247 title "Resonance Raman Spectrum of a ²A_1u Ferryl Porphyrin π-Cation Radical" @default.
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• W1998088247 doi "https://doi.org/10.1021/ja954044x" @default.
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