A comparison of the performance of the semiempirical PM6 method versus DFT methods in Ru-catalyzed olefin metathesis

Andrea Correa*, Albert Poater, Francesco Ragone, Luigi Cavallo

*Corresponding author for this work

Research output: Chapter in Book/Report/Conference proceedingChapterpeer-review

4 Scopus citations

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.

Original languageEnglish (US)
Title of host publicationGreen Metathesis Chemistry
Subtitle of host publicationGreat Challenges in Synthesis, Catalysis and Nanotechnology
PublisherSpringer Verlag
Pages281-292
Number of pages12
ISBN (Print)9789048134311
DOIs
StatePublished - 2010
Externally publishedYes

Publication series

NameNATO Science for Peace and Security Series A: Chemistry and Biology
ISSN (Print)1874-6489

Keywords

  • Ab-initio molecular dynamics
  • Density functional
  • Homogenous catalysis
  • Metathesis
  • Semiemipirical methods
  • Theory calculations

ASJC Scopus subject areas

  • General Chemistry
  • Biochemistry, Genetics and Molecular Biology (miscellaneous)
  • Safety, Risk, Reliability and Quality

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