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

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. One intermediate, two reaction channels: Following the intrinsic reaction coordinates of a Au‐catalysed sigmatropic rearrangement and a protodeauration reaction, two different reaction pathways were found aided by intrinsic bond orbital analysis, showing the versatility of vinyl gold species in the context of catalysis.