On the Lewis Acidity of the Oxoiron(IV) Unit in a Tetramethylcyclam Complex.
The correlation between oxidation state and Lewis acidity is well established for hexaquairon complexes in the +II and +III oxidation state, in which the higher oxidation state leads to a lower pKa for the bound H2 O ligand. This article addresses the Lewis acidity of the oxoiron(IV) complex [FeIV (O)(TMC)(OH2 )]2+ (1-OH2 ; TMC=1,4,8,11-tetramethylcyclam) by determining the pKa of the H2 O ligand. We establish that 1-OH2 has a pKa of 6.9±0.5, a value that falls in between those found for [FeIII (OH2 )6 ]3+ and [FeII (OH2 )6 ]2+ . This intermediate value can be readily rationalized by the presence of the highly basic oxide ligand that mitigates the Lewis acidity of the iron(IV) center. Although the oxo ligand occupies only one position in 1-OH2 , anti to all four methyl groups that protrude from the same face of the nonplanar TMC ligand, its conjugate base 1-OH exists as a mixture of syn and anti tautomers, which are related by proton transfer between the oxo and the hydroxo ligands.