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A Comparison of the Performance of the Semiempirical PM6 Method Versus DFT Methods in Ru-Catalyzed Olefin Metathesis

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Green Metathesis Chemistry

Abstract

In this work we compare the performance of the semiempirical PM6 method with a more accurate DFT method when applied to Ru-catalyzed olefin metathesis. We demonstrate that the PM6 method reproduces with interesting accuracy the geometries located with a DFT approach. As for the energetics, the relative DFT stability of the metallacycle with respect to the coordination intermediate is reproduced with reasonable accuracy by the PM6 method, whereas the olefin coordination energy and the energy barrier of the metathesis step are overestimated. Further, for the same system we performed a PM6-based meta-dynamics study of the olefin metathesis reaction, which indicated a reasonable good behavior of the system also under dynamic conditions. In conclusion, the obtained results validate the use of the semiempirical PM6 method for preliminary and computationally fast screening on new ligands/substrates in Ru catalyzed olefin metathesis.

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Author information

Authors and Affiliations

  1. Department of Chemistry, University of Salerno, via Ponte don Melillo, Fisciano, I-84084, Italy

    Andrea Correa, Albert Poater, Francesco Ragone & Luigi Cavallo

Authors
  1. Andrea Correa
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  2. Albert Poater
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  3. Francesco Ragone
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  4. Luigi Cavallo
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Corresponding author

Correspondence to Andrea Correa .

Editor information

Editors and Affiliations

  1. Romanian Academy, Institute of Organic Chemistry Bucharest, Romania

    Valerian Dragutan  & Ileana Dragutan  & 

  2. University of Liège, Institute of Chemistry Liège, Belgium

    Albert Demonceau

  3. Russian Academy of Sciences Topchiev Institute of Petrochemical Synthesis Moscow, Russia

    Eugene Sh. Finkelshtein

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Correa, A., Poater, A., Ragone, F., Cavallo, L. (2010). A Comparison of the Performance of the Semiempirical PM6 Method Versus DFT Methods in Ru-Catalyzed Olefin Metathesis. In: Dragutan, V., Demonceau, A., Dragutan, I., Finkelshtein, E.S. (eds) Green Metathesis Chemistry. NATO Science for Peace and Security Series A: Chemistry and Biology. Springer, Dordrecht. https://doi.org/10.1007/978-90-481-3433-5_17

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