Oxidative Oligomerization of Phenolic Endocrine Disrupting Chemicals Mediated by Mn(III)‑L Complexes and the Role of Phenoxyl Radicals in the Enhanced Removal: Experimental and Theoretical Studies

Soluble manganese­(III), stabilized by ligands as Mn­(III)-L complexes, are ubiquitous in natural waters and wastewaters and can potentially serve as both the oxidant and reductant in one-electron transfer reactions with organic contaminants. In this study, the oxidative transformations of 14 phenolic endocrine disrupting chemicals (EDCs) by in situ-formed Mn­(III)-L complexes, generated from irradiated water containing Mn­(II) and humic acid, were investigated. The pseudo-first-order rate constants (k obs, h–1) of these phenols varied from 1.0 × 10–4 to 5.9 × 10–2. A quantitative structure–activity relationship model was developed, which suggests that the electron-donating ability (E HOMO) of phenolic chemicals was the most important molecular characteristic for the Mn­(III)-L-mediated oxidative transformation. Phenol transformation was initiated by the generation of a phenoxyl radical through electron transfer to Mn­(III)-L. Subsequent self-coupling reactions between phenoxyl radicals resulted in the formation of self-coupling dimers and trimers. With the addition of simple phenol as a cosubstrate, enhanced transformations of these phenolic EDCs were clearly observed, and cross-coupling products of simple phenol and the substrates were also detected. In addition, a reaction activation energy calculation based on the transition-state theory indicated that the cross-coupling reaction was more likely than the self-coupling reaction to occur in the presence of phenol. This work provides new insights into the environmental fate of phenolic compounds.