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

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.

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chem_201303686_sm_miscellaneous_information.pdf (Supplementary material), 5MB
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chem_201303686_sm_miscellaneous_information.pdf
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Supporting Information
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2014
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Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
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 Creators:
Kozma, Ágnes1, Author           
Deden, Tobias1, Author           
Carreras, Javier1, Author           
Wille, Christian1, Author           
Petuškova, Jekaterina1, Author           
Rust, Jörg2, Author           
Alcarazo, Manuel1, Author           
Affiliations:
1Research Group Alcarazo, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445592              
2Service Department Lehmann (EMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445625              

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Free keywords: cations; cycloisomerization; homogeneous catalysis; phosphines; platinum
 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.

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Language(s): eng - English
 Dates: 2013-09-192014-01-232014-02-17
 Publication Status: Published in print
 Pages: 7
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1002/chem.201303686
 Degree: -

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Title: Chemistry - A European Journal
  Other : Chem. Eur. J.
Source Genre: Journal
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Publ. Info: Weinheim, Germany : VCH Verlagsgesellschaft
Pages: 7 Volume / Issue: 20 (8) Sequence Number: - Start / End Page: 2208 - 2214 Identifier: ISSN: 0947-6539
CoNE: https://pure.mpg.de/cone/journals/resource/954926979058