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Contrary to expectations based on the spectrochemical series, H2O is found to be a significantly weaker field ligand than OH- in the magnetochemical series ranking of ligand field strengths based on the spin states of iron(III) tetraphenylporphyrin complexes. The preparation and characterization of the [Fe(H2O)(TPP)]+ ion and the spectroscopic identification of Fe(OH)(TPP) have made this assessment possible. These two species were previously thought to be unattainable because of the facile formation of the well-known μ-oxo dimer, (TPP)Fe−O−Fe(TPP). However, the special characteristics of single equivalents of water under high acidity, relevant to metalloenzyme active sites and superacidity, make them accessible in benzene solution. Their 1H NMR β-pyrrole chemical shifts at −43 and +82 ppm indicate admixed-intermediate S = 3/2, 5/2 and high S = 5/2 spin states for the aqua and hydroxo species, respectively. The X-ray crystal structure of the aqua complex has been determined for [Fe(H2O)(TPP)][CB11H6Cl6] an...

journal of the american chemical society

Reversal of H<sub>2</sub>O and OH<sup>-</sup> Ligand Field Strength on the Magnetochemical Series Relative to the Spectrochemical Series. Novel 1-equiv Water Chemistry of Iron(III) Tetraphenylporphyrin Complexes

Reversal of H2O and OH- Ligand Field Strength on the Magnetochemical Series Relative to the Spectrochemical Series. Novel 1-equiv Water Chemistry of Iron(III) Tetraphenylporphyrin Complexes

Reversal of H₂O and OH^- Ligand Field Strength on the Magnetochemical Series Relative to the Spectrochemical Series. Novel 1-equiv Water Chemistry of Iron(III) Tetraphenylporphyrin Complexes