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On the accessible reaction channels of vinyl gold(I) species: π- and [sigma]-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 nam...

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Bibliographic Details
Main Authors: Nunes dos Santos Comprido, Laura (Author) , Klein, Johannes E. M. N. (Author) , Knizia, Gerald (Author) , Kästner, Johannes (Author) , Hashmi, A. Stephen K. (Author)
Format: Article (Journal)
Language:English
Published: 19 July 2017
In: Chemistry - a European journal
Year: 2017, Volume: 23, Issue: 45, Pages: 10901-10905
ISSN:1521-3765
DOI:10.1002/chem.201702023
Online Access:Verlag, Volltext: http://dx.doi.org/10.1002/chem.201702023
Verlag, Volltext: http://onlinelibrary.wiley.com/doi/10.1002/chem.201702023/abstract
Verlag, Volltext: http://onlinelibrary.wiley.com/doi/10.1002/chem.201702023/epdf
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Author Notes:Laura Nunes dos Santos Comprido, Johannes E.M.N. Klein, Gerald Knizia, Johannes Kästner, A. Stephen K. Hashmi
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Summary: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.
Item Description:Gesehen am 23.11.2017
Im Zusatz zum Titel sind pi und sigma als griechische Buchstaben dargestellt
Physical Description:Online Resource
ISSN:1521-3765
DOI:10.1002/chem.201702023

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