Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Reactions of Acetyl Radical with Acetylene - A Computational Study

  • Tran, Tu Anh (School of Chemistry and Bio21 Molecular Science and Biotechnology Institute, The University of Melbourne) ;
  • Schiesser, Carl H. (School of Chemistry and Bio21 Molecular Science and Biotechnology Institute, The University of Melbourne)
  • Published : 2010.03.20
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Abstract

Ab initio and DFT molecular orbital calculations predict that acetyl radical reacts with acetylene through interactions primarily involving the SOMO of the radical and the in-plane ${\pi}$-bond of acetylene. An energy barrier (${\Delta}E_1$) of 39.6 kJ $mol^{-1}$ is predicted for the preferred anti arrangement of reactants at the CCSD(T)/cc-pVDZ//BHandHLYP/cc-pVDZ level of theory. NBO analysis reveals additional interactions between the radical SOMO and the nearby C-H ${\sigma}$-bond in acetylene worth about 10% of the total transition state interaction energy. This type of orbital interaction has not previously been observed in radical addition reactions involving C-C ${\pi}$-bonds.

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