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

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 Fe^II(aminobenzenethiolate) and Fe^III(iminobenzenethiolate) forms are readily interconvertible by H⁺/e^- transfer and provide a measure of the bond dissociation free energy (BDFE) for the coordinated N-H bond between 64 and 69 kcal mol^-1. This work shows that coordination to the iron center causes a dramatic weakening of the N-H bond and that Fe- versus S-oxidation in a nonheme iron complex can be controlled by the protonation state of an ancillary amino donor.