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Updated: Jun 23, 2025

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Revisiting the Electron Transfer Mechanisms in Ru(III)-Mediated Advanced Oxidation Processes with Peroxyacids and
Krishnamoorthy Sathiyan1, Junyue Wang2, Lois M Williams1
1Program for Environment and Sustainability, Department of Environmental and Occupational Health, School of Public Health, Texas A&M University, College Station, Texas 77843-8371, United States.
Abstract:
The potential of Ru(III)-mediated advanced oxidation processes has attracted attention due to the recyclable catalysis, high efficiency at circumneutral pHs, and robust resistance against background anions (e.g., phosphate). However, the reactive species in Ru(III)-peracetic acid (PAA) and Ru(III)-ferrate(VI) (FeO42-) systems have not been rigorously examined and were tentatively attributed to organic radicals (CH3C(O)O•/CH3C(O)OO•) and Fe(IV)/Ru(V), representing single electron transfer (SET) and double electron transfer (DET) mechanisms, respectively. Herein, the reaction mechanisms of both systems were investigated by chemical probes, stoichiometry, and electrochemical analysis, revealing different reaction pathways. The negligible contribution of hydroxyl (HO•) and organic (CH3C(O)O•/CH3C(O)OO•) radicals in the Ru(III)-PAA system clearly indicated a DET reaction via oxygen atom transfer (OAT) that produces Ru(V) as the only reactive species. Further, the Ru(III)-performic acid (PFA) system exhibited a similar OAT oxidation mechanism and efficiency. In contrast, the 1:2 stoichiometry and negligible Fe(IV) formation suggested the SET reaction between Ru(III) and ferrate(VI), generating Ru(IV), Ru(V), and Fe(V) as reactive species for micropollutant abatement. Despite the slower oxidation rate constant (kinetically modeled), Ru(V) could contribute comparably as Fe(V) to oxidation due to its higher steady-state concentration. These reaction mechanisms are distinctly different from the previous studies and provide new mechanistic insights into Ru chemistry and Ru(III)-based AOPs.
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