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

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http://pubman.mpdl.mpg.de/cone/persons/resource/persons58476

Carreras,  Javier
Research Group Alcarazo, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons58872

Patil,  Mahendra
Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons59045

Thiel,  Walter
Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons58392

Alcarazo,  M.
Research Group Alcarazo, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Citation

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.


Cite as: http://hdl.handle.net/11858/00-001M-0000-0010-0C4C-A
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.