Mechanisms of Sulfoxidation and Epoxidation Mediated by Iron(III)-Iodosylbenzene Adduct: Electron-Transfer vs. Oxygen-Transfer Mechanism.

The mechanisms of sulfoxidation and epoxidation mediated by previously synthesized and characterized iron(III)-iodosylbenzene adduct, Fe III (OIPh) were investigated using para-substituted thioanisole and styrene derivatives as model substrates. Based on detailed kinetic reaction experiments, including the linear free-energy relationships between the relative reaction rates (log k rel ) and the σ p (4R-PhSMe) with ρ = -0.65 (catalytic) and ρ = -1.13 (stoichiometric), we obtained strong evidence that the stoichiometric and catalytic oxidation of thioanisoles mediated by Fe III (OIPh) species involves direct oxygen transfer. The small negative slope -2.18 from log k obs versus E ox for 4R-PhSMe gives further clear evidence for the direct oxygen atom transfer mechanism. On the contrary, with the linear free-energy relationships between the relative reaction rates (log k rel ) and total substituent effect (TE, 4R-PhCHCH 2 ) parameters with slope = 0.33 (catalytic) and 2.02 (stoichiometric), the stoichiometric and catalytic epoxidation of styrenes takes place through a nonconcerted electron transfer (ET) mechanism, including the formation of the radicaloid benzylic radical intermediate in the rate-determining step. On the basis of mechanistic studies, we came to the conclusion that the title iron(III)-iodosylbenzene complex is able to oxygenate sulfides and alkenes before it is transformed into the oxo-iron form by cleavage of the O-I bond.