Abstract
The potential of vinyl Au species to react either through a controlled pi- or sigma-pathway is demonstrated. This nomenclature is directly derived from the orbitals of the vinyl Au species leading to the newly formed bonds. When the pi-bond of the vinyl Au intermediate is transformed into a sigma-bond, we name it pi-pathway, and a sigma- to sigma- transformation is named s- 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 language | English |
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Pages (from-to) | 10901-10905 |
Number of pages | 5 |
Journal | Chemistry |
Volume | 23 |
Issue number | 45 |
DOIs | |
Publication status | Published - 10-Aug-2017 |
Externally published | Yes |
Keywords
- alkenes
- allyldeauration
- computational chemistry
- gold catalysis
- protodeauration
- CATALYZED CYCLOISOMERIZATION REACTIONS
- DENSITY-FUNCTIONAL THEORY
- CARBENE COMPLEXES
- BASIS-SETS
- STRUCTURAL-CHARACTERIZATION
- ORGANOGOLD COMPLEXES
- ORGANIC-REACTIONS
- CYCLIZATION
- ALKYNES
- BOND