The reaction mechanism and energetics for the conversion of methanol to formaldehyde by an iron-oxo species, FeO+, is investigated. Three competitive reaction pathways for the catalytic reaction are analyzed from DFT computations at the B3LYP level of theory. In Path 1, the H atom of the OH group of methanol is first abstracted by the oxo group of FeO+ via a four-centered transition state (TS1-1) leading to the intermediate complex HO-Fe+-OCH3, and after that one of the H atoms of the OCH3 group is shifted to the OH ligand via a five-centered transition state (TS1-2) to form the final product complex H2O-Fe+-OCH2. In Path 2, one of the H atoms of the CH3 group of methanol is abstracted by the oxo group via a five-centered transition state (TS2-1) leading to the intermediate complex HO-Fe+-OHCH2, and then the H atom of the OHCH2 group is shifted to the OH ligand via a four-centered transition state (TS2-2) to give the product complex. Unlike Paths 1 and 2, which involve a hydrogen shift, the first step in Path 3 involves a methyl migration that takes place via a four-centered transition state (TS3-1) resulting in the formation of the intermediate complex HO-Fe+-OCH3 and the second half of Path 3 is identical to that of Path 1. From B3LYP computations, Path 1 and Path 2 are competitive in energy and Path 3 is unlikely from the energetic viewpoint. Kinetic isotope effects (kH/kD) for the electronic processes of TS1-1, TS2-1, and TS3-1 are computed and analyzed.
All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry