Abstract
Resonance Raman spectra of 15N enriched metallooctaethylporphyrins [M(OEP) − 15N 4] [M = Ni 2+, Fe 3+ (high spin), and Fe 3+ (low spin)] were observed. Polarized Raman lines corresponding to the oxidation state marker band of hemoproteins were observed at 1377 (Ni), 1369 (Fe high spin) and 1372 −1 (Fe low spin) which were shifted to lower frequency from those of the 14N compounds by 6, 5, and 6 cm −1, respectively. The vibrational mode for this band was shown to include an appreciable contribution of the C αN symmetric stretching vibration and to be associated with ca. 0.01 Å of in-phase displacement of the four pyrrole nitrogens toward the metal ion.
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