Insight into the Selective Methylene Oxidation Catalyzed by Mn(CF<sub>3</sub>-PDP)(SbF<sub>6</sub>)<sub>2</sub>/H<sub>2</sub>O<sub>2</sub>/CH<sub>2</sub>ClCO<sub>2</sub>H) System: A DFT Mechanistic Study
Ruihua Zhao, Xiang‐Yu Chen, Zhixiang Wang
Abstract
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.
Topics & Concepts
ChemistryCatalysisMethyleneSelectivityAlcoholManganeseMedicinal chemistryOrganic chemistryMetal-Catalyzed Oxygenation MechanismsCarbon dioxide utilization in catalysisCatalytic Processes in Materials Science