On the Accessible Reaction Channels of Vinyl Gold(I) Species: π- and σ-Pathways

Laura Nunes dos Santos Comprido, Johannes E.M.N. Klein, Gerald Knizia, Johannes Kästner, A. Stephen K. Hashmi

Research output: Contribution to journalArticle

23 Scopus citations

Abstract

The potential of vinyl Au species to react either through a controlled π- or σ-pathway is demonstrated. This nomenclature is directly derived from the orbitals of the vinyl Au species leading to the newly formed bonds. When the π-bond of the vinyl Au intermediate is transformed into a σ-bond, we name it π-pathway, and a σ- to σ- transformation is named σ-pathway. Examples of reactions following these pathways are a Au-catalysed [3,3]-sigmatropic rearrangement and a protodeauration reaction. These reactions have been studied using intrinsic bond orbitals (IBOs) and allow for the clear identification of these pathways. Energies for the reaction path of the Au-catalysed [3,3]-sigmatropic rearrangement were in addition computed using CCSD(T)-F12. Analysis of the intrinsic reaction coordinate (IRC) of the [3,3]-sigmatropic rearrangement using IBOs further allows us to refine the previous mechanistic proposal and identifies a hidden intermediate along the reaction path.

Original languageEnglish (US)
Pages (from-to)10901-10905
Number of pages5
JournalChemistry - A European Journal
Volume23
Issue number45
DOIs
StatePublished - Aug 10 2017

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

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    Nunes dos Santos Comprido, L., Klein, J. E. M. N., Knizia, G., Kästner, J., & Hashmi, A. S. K. (2017). On the Accessible Reaction Channels of Vinyl Gold(I) Species: π- and σ-Pathways. Chemistry - A European Journal, 23(45), 10901-10905. https://doi.org/10.1002/chem.201702023