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On the Accessible Reaction Channels of Vinyl Gold(I) Species: π- and σ-Pathways.
- Source :
-
Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2017 Aug 10; Vol. 23 (45), pp. 10901-10905. Date of Electronic Publication: 2017 Jul 19. - Publication Year :
- 2017
-
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.<br /> (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)
Details
- Language :
- English
- ISSN :
- 1521-3765
- Volume :
- 23
- Issue :
- 45
- Database :
- MEDLINE
- Journal :
- Chemistry (Weinheim an der Bergstrasse, Germany)
- Publication Type :
- Academic Journal
- Accession number :
- 28593697
- Full Text :
- https://doi.org/10.1002/chem.201702023