Proton-promoted oxygen atom transfer vs proton-coupled electron transfer of a non-heme iron(IV)-oxo complex

Sulfoxidation of thioanisoles by a non-heme iron(IV)-oxo complex, (N4Py)Fe(IV)(O)](2+) (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine), was remarkably enhanced by perchloric acid (70% HClO(4)). The observed second-order rate constant (k(obs)) of sulfoxidation of thioaniosoles by (N4Py)Fe(IV)(O)](2+) increases linearly with increasing concentration of HClO(4) (70%) in acetonitrile (MeCN)at 298 K. In contrast to sulfoxidation of thioanisoles by (N4Py)Fe(IV)(O)](2+), the observed second-order rate constant (k(et)) of electron transfer from one-electron reductants such as Fe(II)(Me(2)bpy)(3)](2+) (Me(2)bpy = 4,4-dimehtyl-2,2'-bipyridine) to (N4Py)Fe(IV)(O)](2+) increases with increasing concentration of HClO(4), exhibiting second-order dependence on HClO(4) concentration. This indicates that the proton-coupled electron transfer (PCET) involves two protons associated with electron transfer from Fe(II)(Me(2)bpy)(3)](2+) to (N4Py)Fe(IV)(O)](2+) to yield Fe(III)(Me(2)bpy)(3)](3+) and (N4Py)Fe(III)(OH(2))](3+). The one-electron reduction potential (E(red)) of (N4Py)Fe(IV)(O)](2+) in the presence of 10 mM HClO(4) (70%) in MeCN is determined to be 1.43 V vs SCE. A plot of E(red) vs logHClO(4)] also indicates involvement of two protons in the PCET reduction of (N4Py)Fe(IV)(O)](2+). The PCET driving force dependence of log k(et) is fitted in light of the Marcus theory of outer-sphere electron transfer to afford the reorganization of PCET (λ = 2.74 eV). The comparison of the k(obs) values of acid-promoted sulfoxidation of thioanisoles by (N4Py)Fe(IV)(O)](2+) with the k(et) values of PCET from one-electron reductants to (N4Py)Fe(IV)(O)](2+) at the same PCET driving force reveals that the acid-promoted sulfoxidation proceeds by one-step oxygen atom transfer from (N4Py)Fe(IV)(O)](2+) to thioanisoles rather than outer-sphere PCET.