Journal article

An ab initio and DFT study of homolytic substitution reactions by oxyacyl radicals at sulfur, selenium, and tellurium

Sonia M Horvat, Carl H Schiesser

Tetrahedron | PERGAMON-ELSEVIER SCIENCE LTD | Published : 2012


Homolytic substitution reactions of methoxycarbonyl radicals at the sulfur, selenium, and tellurium atoms in dimethyl sulfide, dimethyl selenide, and dimethyl telluride have been investigated using computational techniques. Ab initio and DFT calculations predict that attack of methoxycarbonyl radical at the sulfur and selenium containing molecules proceed via smooth transition states without the involvement of hypervalent intermediates. BHandHLYP/DZP calculated energy barriers (ΔE ) for these reactions range from 58.3 (S) to 34.6 (Se) kJ mol . In contrast, calculations on the analogous reaction involving tellurium predict the involvement of an intermediate at MP2/DZP. BHandHLYP/DZP calcula..

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University of Melbourne Researchers


Funding Acknowledgements

This work would not have been possible without the generous support of the Australian Research Council through the Centers of Excellence Scheme. We also gratefully acknowledge the support of the National Facility of the Australian National Computational Infrastructure and the School of Chemistry (The University of Melbourne) High Performance Computing facility.