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Issue 30, 2013
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A density functional theory study of the mechanisms of oxidation of ethylene by rhenium oxide complexes

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Abstract

The oxo complexes of group VII B are of great interest for their potential toward epoxidation and dihydroxylation. In this work, the mechanisms of oxidation of ethylene by rhenium-oxo complexes of the type LReO3 (L = O, Cl, CH3, OCH3, Cp, NPH3) have been explored at the B3LYP/LACVP* level of theory. The activation barriers and reaction energies for the stepwise and concerted addition pathways involving multiple spin states have been computed. In the reaction of LReO3 (L = O, Cl, CH3, OCH3, Cp, NPH3) with ethylene, it was found that the concerted [3 + 2] addition pathway on the singlet potential energy surfaces leading to the formation of a dioxylate intermediate is favored over the [2 + 2] addition pathway leading to the formation of a metallaoxetane intermediate and its re-arrangement to form the dioxylate. The activation barrier for the formation of the dioxylate on the singlet PES for the ligands studied is found to follow the order O > CH3 > NPH3 > CH3O > Cl > Cp and the reaction energies follow the order CH3 > O > NPH3 > CH3O > Cl > Cp. On the doublet PES, the [2 + 2] addition leading to the formation the metallaoxetane intermediate is favored over dioxylate formation for the ligands L = CH3, CH3O, Cl. The activation barriers for the formation of the metallaoxetane intermediate are found to increase for the ligands in the order CH3 < Cl < CH3O while the reaction energies follow the order Cl < CH3O < CH3. The subsequent re-arrangement of the metallaoxetane intermediate to the dioxylate is only feasible in the case of ReO3(OCH3). Of all the complexes studied, the best dioxylating catalyst is ReO3Cp (singlet surface); the best epoxidation catalyst is ReO3Cl (singlet surface); and the best metallaoxetane formation catalyst is ReO3(NPH3) (triplet surface).

Graphical abstract: A density functional theory study of the mechanisms of oxidation of ethylene by rhenium oxide complexes

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Publication details

The article was received on 27 Feb 2013, accepted on 30 May 2013 and first published on 30 May 2013


Article type: Paper
DOI: 10.1039/C3DT50539A
Citation: Dalton Trans., 2013,42, 10885-10897
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    A density functional theory study of the mechanisms of oxidation of ethylene by rhenium oxide complexes

    A. Aniagyei, R. Tia and E. Adei, Dalton Trans., 2013, 42, 10885
    DOI: 10.1039/C3DT50539A

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