Effect of Substituted Pyridine Co-Ligands and (Diacetoxyiodo)benzene Oxidants on the Fe(III)-OIPh-Mediated Triphenylmethane Hydroxylation Reaction

Iodosilarene derivatives (PhIO, PhI(OAc)₂) constitute an important class of oxygen atom transfer reagents in organic synthesis and are often used together with iron-based catalysts. Since the factors controlling the ability of iron centers to catalyze alkane hydroxylation are not yet fully understood, the aim of this report is to develop bioinspired non-heme iron catalysts in combination with PhI(OAc)₂, which are suitable for performing C-H activation. Overall, this study provides insight into the iron-based ([Fe^II(PBI)₃(CF₃SO₃)₂] (<b>1</b>), where PBI = 2-(2-pyridyl)benzimidazole) catalytic and stoichiometric hydroxylation of triphenylmethane using PhI(OAc)₂, highlighting the importance of reaction conditions including the effect of the co-ligands (<i>para</i>-substituted pyridines) and oxidants (<i>para</i>-substituted iodosylbenzene diacetates) on product yields and reaction kinetics. A number of mechanistic studies have been carried out on the mechanism of triphenylmethane hydroxylation, including C-H activation, supporting the reactive intermediate, and investigating the effects of equatorial co-ligands and coordinated oxidants. Strong evidence for the electrophilic nature of the reaction was observed based on competitive experiments, which included a Hammett correlation between the relative reaction rate (log<i>k</i>_rel) and the σ_p (4R-Py and 4R'-PhI(OAc)₂) parameters in both stoichiometric (ρ = +0.87 and +0.92) and catalytic (ρ = +0.97 and +0.77) reactions. The presence of [(PBI)₂(4R-Py)Fe^IIIOIPh-4R']³⁺ intermediates, as well as the effect of co-ligands and coordinated oxidants, was supported by their spectral (UV-visible) and redox properties. It has been proven that the electrophilic nature of iron(III)-iodozilarene complexes is crucial in the oxidation reaction of triphenylmethane. The hydroxylation rates showed a linear correlation with the Fe^III/Fe^II redox potentials (in the range of -350 mV and -524 mV), which suggests that the Lewis acidity and redox properties of the metal centers greatly influence the reactivity of the reactive intermediates.