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

DFT study was employed to gain insight into methylene oxidation catalyzed by Mn­(CF₃–PDP)­(NCMe)₂ (SbF₆)₂/H₂O₂/HOAc^Cl(OAC^Cl OC­(O)­CH₂Cl). The active catalyst was characterized to be [Mn]­(O)­OAc^Cl ([Mn]Mn­(CF₃–PDP)²⁺) which is generated via a sequence from [Mn] to [Mn]­OH to [Mn]­OAc^Cl 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.