Resonance Raman studies of carbon monoxide binding to iron "picket fence" porphyrin with unhindered and hindered axial bases. An inverse relationship between binding affinity and the strength of iron-carbon bond.

TLDR: Comparisons of sterically hindered (1,2-Me2Im) and unhindered (N-MeIm) bases are of particular interest because of their implication in the phenomenon of hemoglobin cooperativity and the mechanisms of protein control of heme reactivity.

Abstract: The stretching frequency of the iron-carbon bond, v(Fe-CO), is a direct measure of the iron-carbon bond strength when there is no change in the Fe-C-O geometry. Here we report resonance Raman detection of v(Fe-CO) frequencies in the CO complexes of iron (II) alpha, alpha, alpha, alpha-mesotetrakis(o-pivalamidophenyl)porphyrin, FeII(TpivPP), with trans ligands of varying strength: N-methylimidazole (N-MeIm), 1,2-dimethylimidazole (1,2-Me2Im), pyridine (py), and tetrahydrofuran (THF). It was found that the weaker the iron-trans ligand bond, the stronger the iron-carbon bond. Comparisons of sterically hindered (1,2-Me2Im) and unhindered (N-MeIm) bases are of particular interest because of their implication in the phenomenon of hemoglobin cooperativity and the mechanisms of protein control of heme reactivity. While the CO binding affinity of FeII(TpivPP)(1,2-MeIm) is approximately 400 times lower than that of FeII(TpivPP)(N-MeIm), the v(Fe-CO) frequency for the former (at 496 cm-1) is higher than that for the latter (at 489 cm-1). This example shows that the CO binding affinity cannot be directly correlated with the strength of the iron-carbon bond. Comparison of the CO binding to FeII(TpivPP)(THF) and FeII(TpivPP)(N-MeIm) reveals a similar relationship; the v(Fe-CO) frequency (at 527 cm-1) in FeII(TpivPP)(THF)(CO) is 38 cm-1 higher than that in FeII(TpivPP)(N-MeIm)(CO), but the CO binding affinity is lower for the THF complex.