Proton-Coupled Electron-Transfer Reactivity Controls Iron versus Sulfur Oxidation in Nonheme Iron-Thiolate Complexes.

ABSTRACT: Reaction of the five-coordinate Fe^II(N₄S) complexes, [Fe^II(iPr₃TACN)(abt^X)](OTf) (abt = aminobenzenethiolate, X = H, CF₃), with a one-electron oxidant and an appropriate base leads to net H atom loss, generating new Fe^III(iminobenzenethiolate) complexes that were characterized by single-crystal X-ray diffraction (XRD), as well as UV-vis, EPR, and Mössbauer spectroscopies. The spectroscopic data indicate that the iminobenzenethiolate complexes have S = 3/2 ground states. In the absence of a base, oxidation of the Fe^II(abt) complexes leads to disulfide formation instead of oxidation at the metal center. Bracketing studies with separated proton-coupled electron-transfer (PCET) reagents show that the

SUBMITTER: Gordon JB 

PROVIDER: S-EPMC8139613 | biostudies-literature | 2021 May

REPOSITORIES: biostudies-literature