Electrochemically Generated cis-Carboxylato-Coordinated Iron(IV) Oxo Acid-Base Congeners as Promiscuous Oxidants of Water Pollutants.

The nonheme iron(IV) oxo complex [FeIV(O)(tpenaH)]2+ and its conjugate base [FeIV(O)(tpena)]+ [tpena- = N,N,N'-tris(2-pyridylmethyl)ethylenediamine-N'-acetate] have been prepared electrochemically in water by bulk electrolysis of solutions prepared from [FeIII2(μ-O)(tpenaH)2](ClO4)4 at potentials over 1.3 V (vs NHE) using inexpensive and commercially available carbon-based electrodes. Once generated, these iron(IV) oxo complexes persist at room temperature for minutes to half an hour over a wide range of pH values. They are capable of rapidly decomposing aliphatic and aromatic alcohols, alkanes, formic acid, phenols, and the xanthene dye rhodamine B. The oxidation of formic acid to carbon dioxide demonstrates the capacity for total mineralization of organic compounds. A radical hydrogen-atom-abstraction mechanism is proposed with a reactivity profile for the series that is reminiscent of oxidations by the hydroxyl radical. Facile regeneration of [FeIV(O)(tpenaH)]2+/ [FeIV(O)(tpena)]+ and catalytic turnover in the oxidation of cyclohexanol under continuous electrolysis demonstrates the potential of the application of [FeIII(tpena)]2+ as an electrocatalyst. The promiscuity of the electrochemically generated iron(IV) oxo complexes, in terms of the broad range of substrates examined, represents an important step toward the goal of cost-effective electrocatalytic water purification.