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  Exploiting the π-Acceptor Properties of Carbene-Stabilized Phosphorus Centered Trications [L3P] 3+: Applications in Pt(II) Catalysis

Carreras, J., Patil, M., Thiel, W., & Alcarazo, M. (2012). Exploiting the π-Acceptor Properties of Carbene-Stabilized Phosphorus Centered Trications [L3P] 3+: Applications in Pt(II) Catalysis. Journal of the American Chemical Society, 134(40), 16753-16758. doi:10.1021/ja306947m.

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 Creators:
Carreras, Javier1, Author              
Patil, Mahendra2, Author              
Thiel, Walter2, Author              
Alcarazo, M.1, Author              
Affiliations:
1Research Group Alcarazo, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445592              
2Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445590              

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 Abstract: Reaction of tris(dimethylaminocyclopropenium) substituted phosphine 1 with K2PtCl4 afforded the bench stable complex 3 which upon treatment with Ag[CB11H6Cl6] turned out to be an excellent catalyst for the transformation of a variety of ortho-biaryl substituted alkynes into polycyclic homo- and heteroarenes of different size, shape, and curvature through a 6-endo-dig cyclization. This constitutes the first example ever reported of using a P1-centered trication as ligand in catalysis. The strong π-acceptor character of 1 that derives from its three positive charges substantially increases the intrinsic π-acidity of Pt in complex 1·PtCl2 and dramatically enhances its ability to activate π-systems toward nucleophilic attack. As a consequence, a remarkable acceleration of the model transformation is observed when compared with other classical π-acceptor ligands such as P(OPh)3 or P(C6F5)3. Moreover, the employment of 1 as ligand also expands the scope of this reaction to previously inaccessible substitution patterns. Kinetic studies and deuterium labeling experiments as well as density functional theory (DFT) calculations were performed in order to explain these findings.

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Language(s): eng - English
 Dates: 2012-07-162012-09-252012-10-10
 Publication Status: Published in print
 Pages: 6
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/ja306947m
 Degree: -

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Title: Journal of the American Chemical Society
  Other : J. Am. Chem. Soc.
Source Genre: Journal
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Publ. Info: American Chemical Society
Pages: 6 Volume / Issue: 134 (40) Sequence Number: - Start / End Page: 16753 - 16758 Identifier: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870
DOI: 10.1021/ja306947m