• Login
    View Item 
    •   Home
    • Research
    • Articles
    • View Item
    •   Home
    • Research
    • Articles
    • View Item
    JavaScript is disabled for your browser. Some features of this site may not work without it.

    Browse

    All of KAUSTCommunitiesIssue DateSubmit DateThis CollectionIssue DateSubmit Date

    My Account

    Login

    Quick Links

    Open Access PolicyORCID LibguideTheses and Dissertations LibguideSubmit an Item

    Statistics

    Display statistics

    Controlled acrylate insertion regioselectivity in diazaphospholidine- sulfonato palladium(II) complexes

    • CSV
    • RefMan
    • EndNote
    • BibTex
    • RefWorks
    Type
    Article
    Authors
    Wucher, Philipp
    Roesle, Philipp
    Falivene, Laura cc
    Cavallo, Luigi cc
    Caporaso, Lucia cc
    Göttker-Schnetmann, Inigo J.
    Mecking, Stefan
    KAUST Department
    Biological and Environmental Sciences and Engineering (BESE) Division
    Chemical Science Program
    KAUST Catalysis Center (KCC)
    Physical Science and Engineering (PSE) Division
    Date
    2012-12-07
    Online Publication Date
    2012-12-07
    Print Publication Date
    2012-12-24
    Permanent link to this record
    http://hdl.handle.net/10754/562465
    
    Metadata
    Show full item record
    Abstract
    Diazaphospholidine-sulfonato Pd(II) complexes [{κ2-P,O-(N- Ar2C2H4N2P)C6H 4SO3}PdMe(L)] 1-L (L = dmso, pyridine, lutidine, or μ-LiCl(solvent); 1a: Ar = Ph, 1b: Ar = 2-MeC6H4, 1c: Ar = 2-MeOC6H4, 1d: Ar = 2,4,6-Me3C 6H2, 1e: Ar = 2,6-iPr2C6H 3, 1f: Ar = 2,6-(p-tolyl)2C6H3) were prepared and structurally characterized. The regioselectivity of methyl acrylate (MA) insertion into the Pd-Me bond is entirely inverted from >93% 1,2-insertion for bulky substituents (1d-f, yielding the insertion products [(P̂O)Pd{κ2-C,O-CH2CHMeC(O)OMe], 12) to the usual electronically controlled 2,1-insertion (>95%) for the less bulky Ar = Ph (1a, yielding the insertion product [(P̂O)Pd{κ2-C,O- CHEtC(O)OMe], 11, and β-H elimination product methyl crotonate). DFT studies underline that this is due to a more favorable insertion transition state (2,1- favored by 12 kJ mol-1 over 1,2- for 1a) vs destabilization of the 2,1-insertion transition state in 1d,e. By contrast, MA insertion into the novel isolated and structurally characterized hydride and deuteride complexes [{κ2-P,O-(N-Ar2C 2H4N2P)C6H4SO 3}PdR(lutidine)] (Ar = 2,6-iPr2C6H3; 9e: R = H, 10e: R = D) occurs 2,1-selectively. This is due to the insertion occurring from the isomer with the P-donor and the olefin in trans arrangement, rather than the insertion into the alkyl from the cis isomer in which the olefin is in proximity to the bulky diazaphospholidine. 1a-f are precursors to active catalysts for ethylene polymerization to highly linear polyethylene with M n up to 35 000 g mol-1. In copolymerization experiments, norbornene was incorporated in up to 6.1 mol % into the polyethylene backbone. © 2012 American Chemical Society.
    Citation
    Wucher, P., Roesle, P., Falivene, L., Cavallo, L., Caporaso, L., Göttker-Schnetmann, I., & Mecking, S. (2012). Controlled Acrylate Insertion Regioselectivity in Diazaphospholidine-Sulfonato Palladium(II) Complexes. Organometallics, 31(24), 8505–8515. doi:10.1021/om300755j
    Sponsors
    Financial support by the DFG (Me1388/10-1) is gratefully acknowledged. The authors thank Lars Bolk for GPC, Anke Friemel and Ulrich Haunz for support with NMR measurements, and the HPC team of Enea (www.enea.it) for use of the ENEA-GRID and the HPC facilities CRESCO (www.cresco.enea.it) in Portici, Italy.
    Publisher
    American Chemical Society (ACS)
    Journal
    Organometallics
    DOI
    10.1021/om300755j
    Relations
    Is Supplemented By:
    • [Dataset]
      Wucher, P., Roesle, P., Falivene, L., Cavallo, L., Caporaso, L., Göttker-Schnetmann, I., & Mecking, S. (2013). CCDC 894982: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccz19dp. DOI: 10.5517/ccz19dp HANDLE: 10754/624732
    • [Dataset]
      Wucher, P., Roesle, P., Falivene, L., Cavallo, L., Caporaso, L., Göttker-Schnetmann, I., & Mecking, S. (2013). CCDC 894983: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccz19fq. DOI: 10.5517/ccz19fq HANDLE: 10754/624733
    • [Dataset]
      Wucher, P., Roesle, P., Falivene, L., Cavallo, L., Caporaso, L., Göttker-Schnetmann, I., & Mecking, S. (2013). CCDC 894984: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccz19gr. DOI: 10.5517/ccz19gr HANDLE: 10754/624734
    • [Dataset]
      Wucher, P., Roesle, P., Falivene, L., Cavallo, L., Caporaso, L., Göttker-Schnetmann, I., & Mecking, S. (2013). CCDC 894985: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccz19hs. DOI: 10.5517/ccz19hs HANDLE: 10754/624735
    • [Dataset]
      Wucher, P., Roesle, P., Falivene, L., Cavallo, L., Caporaso, L., Göttker-Schnetmann, I., & Mecking, S. (2013). CCDC 894986: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccz19jt. DOI: 10.5517/ccz19jt HANDLE: 10754/624736
    • [Dataset]
      Wucher, P., Roesle, P., Falivene, L., Cavallo, L., Caporaso, L., Göttker-Schnetmann, I., & Mecking, S. (2013). CCDC 894987: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccz19kv. DOI: 10.5517/ccz19kv HANDLE: 10754/624737
    • [Dataset]
      Wucher, P., Roesle, P., Falivene, L., Cavallo, L., Caporaso, L., Göttker-Schnetmann, I., & Mecking, S. (2013). CCDC 894988: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccz19lw. DOI: 10.5517/ccz19lw HANDLE: 10754/624738
    • [Dataset]
      Wucher, P., Roesle, P., Falivene, L., Cavallo, L., Caporaso, L., Göttker-Schnetmann, I., & Mecking, S. (2013). CCDC 894989: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccz19mx. DOI: 10.5517/ccz19mx HANDLE: 10754/624739
    • [Dataset]
      Wucher, P., Roesle, P., Falivene, L., Cavallo, L., Caporaso, L., Göttker-Schnetmann, I., & Mecking, S. (2013). CCDC 894990: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccz19ny. DOI: 10.5517/ccz19ny HANDLE: 10754/624740
    • [Dataset]
      Wucher, P., Roesle, P., Falivene, L., Cavallo, L., Caporaso, L., Göttker-Schnetmann, I., & Mecking, S. (2013). CCDC 894991: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccz19pz. DOI: 10.5517/ccz19pz HANDLE: 10754/624741
    ae974a485f413a2113503eed53cd6c53
    10.1021/om300755j
    Scopus Count
    Collections
    Articles; Biological and Environmental Science and Engineering (BESE) Division; Physical Science and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

    entitlement

     
    DSpace software copyright © 2002-2022  DuraSpace
    Quick Guide | Contact Us | KAUST University Library
    Open Repository is a service hosted by 
    Atmire NV
     

    Export search results

    The export option will allow you to export the current search results of the entered query to a file. Different formats are available for download. To export the items, click on the button corresponding with the preferred download format.

    By default, clicking on the export buttons will result in a download of the allowed maximum amount of items. For anonymous users the allowed maximum amount is 50 search results.

    To select a subset of the search results, click "Selective Export" button and make a selection of the items you want to export. The amount of items that can be exported at once is similarly restricted as the full export.

    After making a selection, click one of the export format buttons. The amount of items that will be exported is indicated in the bubble next to export format.