Intramolecular anti‐Phosphinoauration of Alkynes: An FLP‐Motivated Approach to Stable Aurated Phosphindolium Complexes

The synthesis of aurated phosphindolium complexes from easy accessible 1,5‐alkynylphosphine derivatives has been studied by using gold(I) complexes featuring carbene and phosphine ligands as initiators. Upon formation of the mixed phosphine NHC/phosphine gold species, elevated temperatures induced t...

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Bibliographic Details
Published in:Chemistry : a European journal 2017-02, Vol.23 (11), p.2542-2547
Main Authors: Arndt, Sebastian, Hansmann, Max M., Motloch, Petr, Rudolph, Matthias, Rominger, Frank, Hashmi, A. Stephen K.
Format: Article
Language:English
Subjects:
Accessibility
Alkynes
Chemistry
Derivatives
frustrated lewis pair
Gold
Ligands
Mathematical analysis
Phosphines
Synthesis
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Summary:The synthesis of aurated phosphindolium complexes from easy accessible 1,5‐alkynylphosphine derivatives has been studied by using gold(I) complexes featuring carbene and phosphine ligands as initiators. Upon formation of the mixed phosphine NHC/phosphine gold species, elevated temperatures induced the cyclization to give stable aurated phosphindolium salts, which is supported by DFT calculations. The key elementary step that comprises a yet unknown anti‐phosphinoauration of an unactivated alkyne is favored if bulky NHC ligands are used which was analyzed by kinetic measurements. This concept could furthermore be extended to neutral (phosphindolium)AuCl complexes featuring the yet unknown phosphindole ligand. Phosphinoauration: Aurated phosphindolium complexes are synthesized from ortho‐phosphane phenylacetylene derivatives by an anti‐phosphinoauration reaction. This new elementary step in gold catalysis is favored if bulky ligands are used at the gold center, which is in accord with the concept of Frustrated Lewis Pair (FLP) chemistry.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201605914