Issue 8, 2010
From the journal:

New Journal of Chemistry

An ab initio and DFT study of homolytic substitution reactions of acyl radicals at sulfur, selenium, and tellurium†‡

Sonia M. Horvat*ab  and  Carl H. Schiesserab  

* Corresponding authors

a School of Chemistry, The University of Melbourne, Victoria, Australia
E-mail: shorvat@unimelb.edu.au

b Bio21 Molecular Science and Biotechnology Institute, The University of Melbourne, Victoria, Australia

Abstract

Ab initio calculations using the 6-311G**, cc-pVDZ, aug-cc-pVDZ, and (valence) double-ζ pseudopotential (DZP) basis sets, with (MP2, ROMP2, QCISD, CCSD(T)) and without (HF) the inclusion of electron correlation, and density functional (BHandHLYP and B3LYP) calculations predict that homolytic substitution reactions of acetyl radicals at the sulfur, selenium and tellurium atoms in dimethyl sulfide, dimethyl selenide, and dimethyl telluride adopt an almost collinear arrangement of attacking and leaving radicals at the chalcogen atom. Energy barriers (ΔE‡) for these reactions range from 76.5 (attack at S, BHandHLYP/6-311G**) to 35.5 kJ mol−1 (attack at Te, BHandHLYP/DZP). While the calculated energy barriers for the forward and reverse energy barriers for substitution of acetyl radical at the sulfur atom are comparable, the reverse reactions are favoured by 3–14 kJ mol−1 for attack at selenium and by 20–25 kJ mol−1 for attack at tellurium.

Graphical abstract: An ab initio and DFT study of homolytic substitution reactions of acyl radicals at sulfur, selenium, and tellurium

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Article information

DOI
https://doi.org/10.1039/C0NJ00125B
Article type
Paper
Submitted
16 Feb 2010
Accepted
27 Apr 2010
First published
03 Jun 2010

New J. Chem., 2010,34, 1692-1699

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

S. M. Horvat and C. H. Schiesser, New J. Chem., 2010, 34, 1692 DOI: 10.1039/C0NJ00125B

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