NaClO-Generated Iron(IV)oxo and Iron(V)oxo TAMLs in Pure Water

The unique properties of entirely aliphatic TAML activator [Fe^III{(Me₂CNCOCMe₂NCO)₂CMe₂}OH₂]^- (3), namely the increased steric bulk of the ligand and the unmatched resistance to the acid-induced demetalation, enables the generation of high-valent iron derivatives in pure water at any pH. An iron(V)oxo species is readily produced with NaClO at pH values from 2 to 10.6 without any observable intermediate. This is the first reported example of iron(V)oxo formed in pure water. At pH 13, iron(V)oxo is not formed and NaClO oxidizes 3 to an iron(IV)oxo derivative.