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

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journal contribution
posted on 10.10.2016, 00:00 by Matthew R. Mills, Andrew C. Weitz, Michael P. Hendrich, Alexander D. Ryabov, Terrence J. Collins
The unique properties of entirely aliphatic TAML activator [FeIII{(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.