Proton-promoted disproportionation of iron(V)-imido TAML to iron(V)-imido TAML cation radical and iron(IV) TAML.

The present study reports the first example of a proton-promoted disproportionation reaction of a non-heme iron(v)-imido TAML (1) complex to give an iron(v)-imido TAML cation radical (2) and an iron(iv) TAML (3) upon addition of acids. Detailed mechanistic investigations revealed that two molecules of 1 react with one proton to yield 2 and [FeIV(NHTs)(TAML)]- (4), followed by the reaction of 4 with another proton to afford 3 and NH2Ts.