Abstract
Resonance Raman (RR) spectroscopy capable of providing much information about the strength of Fe-ligand bonds in heme proteins has been applied to the study of the Fe-OH bond. The first observations and assignment of nu(Fe-OH) and {nu}{sub sym}(Fe-(OH){sub 2}) stretching bonds are reported herein. It has also been demonstrated that the bis(hydroxo)complex constitutes an S=5/2, S=1/2 spin equilibrium that is reminiscent of alkaline met myoglobin. The RR, NMR, and ESR data provide consistent and compelling evidence for the existence of primarily three coordination states of the (tetrakis(2-N-methylpyridiniumyl)-porphinato) iron (III), Fe(T(2-N-Me)PyP){sup 5+} (aq) ion in solutions of varying pH. At low pH values, a high-spin aquo complex exists; while at intermediate pH values, a high-spin 5-coordinate mono(hydroxo) complex was found. A high-spin/low-spin equilibrium of bis(hydroxide) species was noted at high pH values. 23 refs., 4 figs.
Published Version
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