Browsing by Author "Kwawu, Caroline"

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    Permanganyl chloride-mediated oxidation of tetramethylethylene: Adensity functional theory study
    (Elsevier Inc., 2020-04-08) Aniagyei, Albert; Kwawu, Caroline; Tia, Richard; Adei, Evans
    The mechanisms of the oxidation of tetramethylethylene (TME) by permanganyl chloride (MnO3Cl) havebeen explored on the singlet and triplet potential energy surfaces at the B3LYP LANL2DZ/6-31G (d) levelof theory. The results show that the pathway leading to the formation of thefive-membered dioxylatethrough concerted [3þ2] addition is favored kinetically and thermodynamically over the three otherpossible pathways, namely the [2þ2] addition via the transient metallaoxetane intermediate, epoxi-dation, and hydrogen transfer pathways. The epoxide precursor that on hydrolysis would yield theepoxide product will most likely arise from a stepwise path through the intermediacy of an organo-metallic intermediate. This pathway affords the product that is more stable (thermodynamically favor-able). However, kinetically, both the stepwise and the concerted [2þ1] addition pathways leading to theepoxide precursors are very competitive (activation barrier difference of<0.7 kcal/mol).