American Chemical Society
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Insight into the Selective Methylene Oxidation Catalyzed by Mn(CF3‑PDP)(SbF6)2/H2O2/CH2ClCO2H) System: A DFT Mechanistic Study

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journal contribution
posted on 2021-02-15, 21:04 authored by Ruihua Zhao, Xiang-Yu Chen, Zhi-Xiang Wang
DFT study was employed to gain insight into methylene oxidation catalyzed by Mn­(CF3–PDP)­(NCMe)2 (SbF6)2/H2O2/HOAcCl(OACCl OC­(O)­CH2Cl). The active catalyst was characterized to be [Mn]­(O)­OAcCl ([Mn]Mn­(CF3–PDP)2+) which is generated via a sequence from [Mn] to [Mn]­OH to [Mn]­OAcCl to [Mn]­OOH. With the active catalyst, the methylene group is sequentially oxidized to an alcohol and then to a carbonyl group via rebound mechanism. The mechanism explains the observed site selectivity.