On the accessible reaction channels of vinyl gold(I) species

• Verfasst von: Nunes dos Santos Comprido, Laura [VerfasserIn]
• Verfasst von: Klein, Johannes E. M. N. [VerfasserIn]
• Verfasst von: Knizia, Gerald [VerfasserIn]
• Verfasst von: Kästner, Johannes [VerfasserIn]
• Verfasst von: Hashmi, A. Stephen K. [VerfasserIn]
• Titel: On the accessible reaction channels of vinyl gold(I) species
• Titelzusatz: π- and [sigma]-pathways
• Verf.angabe: Laura Nunes dos Santos Comprido, Johannes E.M.N. Klein, Gerald Knizia, Johannes Kästner, A. Stephen K. Hashmi
• Umfang: 5 S.
• Fussnoten: Gesehen am 23.11.2017 ; Im Zusatz zum Titel sind pi und sigma als griechische Buchstaben dargestellt
• Titel Quelle: Enthalten in: Chemistry - a European journal
• Jahr Quelle: 2017
• Band/Heft Quelle: 23(2017), 45, S. 10901-10905
• ISSN Quelle: 1521-3765
• DOI: doi:10.1002/chem.201702023
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1565639510

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.