A theoretical study on the reaction mechanisms of the addition of transition metal oxo complexes of the type MO3Cl (M = Mn, Tc, and Re) to tetramethylethylene (TME) is presented. Theoretical calculations using B3LYP/LACVP* and M06/LACVP* (LACVP* is a combination of the 6-31G(d) basis set along with LANL2DZ pseudopotentials on the metallic centres) were performed and the results are discussed within the framework of reaction energetics. The nature of the stability of the reaction mechanisms was equivalent for both theories. However, the M06/LACVP* simulations generally had slightly lower energies and shorter bond lengths compared to the B3LYP/LACVP* computations.

Furthermore, it was observed that the reaction does not proceed via the stepwise reaction mechanism due to kinetic and thermodynamic instabilities. Epoxidation was also found to occur via the [2 + 2] concerted reaction mechanism for the MO3Cl (M = Tc and Re) whereas the permanganyl chloride complex epoxidizes TME via the [2 + 1] concerted reaction mechanism on the singlet potential energy surface (PES). Dioxylation was observed to proceed via the [3 + 2] route for the addition of MO3Cl (M = Tc and Re) and TME. Results indicate that all reaction surfaces were unselective except for the permanganyl chloride catalyzed surface which leads to the formation of epoxides exclusively.

Changes in temperatures from 298.15 K to 373.15 K, resulted in kinetically and thermodynamically unstable reaction pathways as the activation and reaction energies increased generally. On the singlet PES, the rate constant calculations showed that the [3 + 2] catalyzed surface reaction mechanism leading to dioxylation was faster than the [2 + 2] mechanism in cases where plausible.

Theoretical values from the global reactivity parameters, namely the chemical hardness, chemical potential, electrophilic and nucleophilic indices, are in good correlation with the DFT activation and reaction energies at both levels of theories. Thus, as the electrophilic nature of the metal decreases from Mn to Re, so do the activation and reaction energies increase from Mn to Re, indicating that the higher the electrophilicity of the metal centre, the more spontaneous the oxidation reaction.