Abstract
Vibrational relaxation of carbon monoxide bound to a series of metalloporphyrin complexes (M-(coproporphyrinate-I tetraisopropyl ester)(CO)(pyridine); M = Fe, Ru, Os) was measured using picosecond infrared pump-probe experiments. The vibrational relaxation rates ((1–2.5) × 10 10 s −1) increased with increasing mass of the metal ion. This effect is opposite that predicted by through-σ-bond models and is interpreted as arising from a through-π-bond coupling between the CO vibrational fundamental and porphyrin vibrations.
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