de.mpg.escidoc.pubman.appbase.FacesBean
English
 
Help Guide Disclaimer Contact us Login
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT

Released

Journal Article

Coordination Chemistry of Cyclopropenylidene-Stabilized Phosphenium Cations: Synthesis and Reactivity of Pd and Pt Complexes

MPS-Authors
http://pubman.mpdl.mpg.de/cone/persons/resource/persons101536

Kozma,  Ágnes
Research Group Alcarazo, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons132978

Deden,  Tobias
Research Group Alcarazo, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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/persons59112

Wille,  Christian
Research Group Alcarazo, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons58884

Petuškova,  Jekaterina
Research Group Alcarazo, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons58946

Rust,  Jörg
Service Department Lehmann (EMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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

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

Locator
There are no locators available
Fulltext (public)
There are no public fulltexts available
Supplementary Material (public)

chem_201303686_sm_miscellaneous_information.pdf
(Supplementary material), 5MB

Citation

Kozma, Á., Deden, T., Carreras, J., Wille, C., Petuškova, J., Rust, J., et al. (2014). Coordination Chemistry of Cyclopropenylidene-Stabilized Phosphenium Cations: Synthesis and Reactivity of Pd and Pt Complexes. Chemistry - A European Journal, 20(8), 2208-2214. doi:10.1002/chem.201303686.


Cite as: http://hdl.handle.net/11858/00-001M-0000-0018-B23B-E
Abstract
A straightforward synthesis of cyclopropenylidene-stabilized phosphenium cations 1 a–g through the reaction of [(iPr2N)2C3+Cl]BF4 with secondary phosphines is described. Their donor ability was evaluated by analysis of the CO stretching frequency in Rh complexes [RhCl(CO)L2](BF4)2 and electrochemical methods. The cyclopropenium ring induces a phosphite-type behavior that can be tuned by the other two substituents attached to the phosphorus atom. Despite of the positive charge that they bear, phosphenium cations 1 a–g still act as two-electron donor ligands, forming adducts with PdII and PtII precursors. Conversely, in the presence of Pd0 species, an oxidative insertion of the Pd atom into the Ccarbene–phosphorus bond takes place, providing dimeric structures in which each Pd atom is bonded to a cyclopropenyl carbene while two dialkyl/diaryl phosphide ligands serve as bridges between the two Pd centers. The catalytic performance of the resulting library of PtII complexes was tested; all of the cationic phosphines accelerated the prototype 6-endo-dig cyclization of 2-ethynyl-1,1′-biphenyl to afford pentahelicene. The best ligand 1 g was used in the synthesis of two natural products, chrysotoxene and epimedoicarisoside A.