A Synthetically Generated LFe^IVOH _n Complex

High-valent Fe-OH species are important intermediates in hydroxylation chemistry. Such complexes have been implicated in mechanisms of oxygen-activating enzymes and have thus far been observed in Compound II of sulfur-ligated heme enzymes like cytochrome P450. Attempts to synthetically model such species have thus far seen relatively little success. Here, the first synthetic Fe^IVOH _n complex has been generated and spectroscopically characterized as either [LFe^IVOH]^- or [LFe^IVOH₂]⁰, where H₄L = Me₄C₂(NHCOCMe₂NHCO)₂CMe₂ is a variant of a tetra-amido macrocyclic ligand (TAML). The steric bulk provided by the replacement of the aryl group with the -CMe₂CMe₂- unit in this TAML variant prevents dimerization in all oxidation states over a wide pH range, thus allowing the generation of Fe^IVOH _n in near quantitative yield from oxidation of the [LFe^IIIOH₂]^- precursor.