Computational study on chain pathways for oxygen atom transfer catalyzed by a methyl(dithiolate) thiorhenium(V) compound

Models of dithiolate Re(V) oxo and thio complexes that catalyze oxygen atom transfer (OAT) reactions have been examined computationally using B3LYP in an effort to understand the mechanism of Re(V)thio complex (2) in comparison with Re(V) oxo complex ( 1 in Chart 1 ). The B3LYP shows that Re(VII)OS and the six-coordinated intermediates ( I 2 , Chart 2 ) cannot be formed during the catalytic process of catalysis 2 as previously proposed. A modified non-radical chain mechanism has been proposed to explain the experimental and the computational results. The modified mechanism does not include the Re(VII)OS as intermediate during the OAT process.