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    A comprehensive mechanistic picture of the isomerizing alkoxycarbonylation of plant oils

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    Type
    Article
    Authors
    Roesle, Philipp
    Caporaso, Lucia cc
    Schnitte, Manuel
    Goldbach, Verena
    Cavallo, Luigi cc
    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
    2014-11-21
    Online Publication Date
    2014-11-21
    Print Publication Date
    2014-12-03
    Permanent link to this record
    http://hdl.handle.net/10754/563911
    
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    Abstract
    Theoretical studies on the overall catalytic cycle of isomerizing alkoxycarbonylation reveal the steric congestion around the diphosphine coordinated Pd-center as decisive for selectivity and productivity. The energy profile of isomerization is flat with diphosphines of variable steric bulk, but the preference for the formation of the linear Pd-alkyl species is more pronounced with sterically demanding diphosphines. CO insertion is feasible and reversible for all Pd-alkyl species studied and only little affected by the diphosphine. The overall rate-limiting step associated with the highest energetic barrier is methanolysis of the Pd-acyl species. Considering methanolysis of the linear Pd-acyl species, whose energetic barrier is lowest within all the Pd-acyl species studied, the barrier is calculated to be lower for more congesting diphosphines. Calculations indicate that energy differences of methanolysis of the linear versus branched Pd-acyls are more pronounced for more bulky diphosphines, due to involvement of different numbers of methanol molecules in the transition state. Experimental studies under pressure reactor conditions showed a faster conversion of shorter chain olefin substrates, but virtually no effect of the double bond position within the substrate. Compared to higher olefins, ethylene carbonylation under identical conditions is much faster, likely due not just to the occurrence of reactive linear acyls exclusively but also to an intrinsically favorable insertion reactivity of the olefin. The alcoholysis reaction is slowed down for higher alcohols, evidenced by pressure reactor and NMR studies. Multiple unsaturated fatty acids were observed to form a terminal Pd-allyl species upon reaction with the catalytically active Pd-hydride species. This process and further carbonylation are slow compared to isomerizing methoxycarbonylation of monounsaturated fatty acids, but selective.
    Citation
    Roesle, P., Caporaso, L., Schnitte, M., Goldbach, V., Cavallo, L., & Mecking, S. (2014). A Comprehensive Mechanistic Picture of the Isomerizing Alkoxycarbonylation of Plant Oils. Journal of the American Chemical Society, 136(48), 16871–16881. doi:10.1021/ja508447d
    Sponsors
    P.R. gratefully acknowledges support from the Carl-Zeiss-Foundation by a graduate fellowship. We thank Dako AG for donation of high-oleic sunflower oils.
    Publisher
    American Chemical Society (ACS)
    Journal
    Journal of the American Chemical Society
    DOI
    10.1021/ja508447d
    Relations
    Is Supplemented By:
    • [Dataset]
      Roesle, P., Caporaso, L., Schnitte, M., Goldbach, V., Cavallo, L., & Mecking, S. (2015). CCDC 1010345: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc12xbs3. DOI: 10.5517/cc12xbs3 HANDLE: 10754/624344
    • [Dataset]
      Roesle, P., Caporaso, L., Schnitte, M., Goldbach, V., Cavallo, L., & Mecking, S. (2015). CCDC 1010346: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc12xbt4. DOI: 10.5517/cc12xbt4 HANDLE: 10754/624345
    • [Dataset]
      Roesle, P., Caporaso, L., Schnitte, M., Goldbach, V., Cavallo, L., & Mecking, S. (2015). CCDC 1010347: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc12xbv5. DOI: 10.5517/cc12xbv5 HANDLE: 10754/624346
    • [Dataset]
      Roesle, P., Caporaso, L., Schnitte, M., Goldbach, V., Cavallo, L., & Mecking, S. (2015). CCDC 1010348: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc12xbw6. DOI: 10.5517/cc12xbw6 HANDLE: 10754/624347
    • [Dataset]
      Roesle, P., Caporaso, L., Schnitte, M., Goldbach, V., Cavallo, L., & Mecking, S. (2015). CCDC 1010349: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc12xbx7. DOI: 10.5517/cc12xbx7 HANDLE: 10754/624348
    • [Dataset]
      Roesle, P., Caporaso, L., Schnitte, M., Goldbach, V., Cavallo, L., & Mecking, S. (2015). CCDC 1010350: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc12xby8. DOI: 10.5517/cc12xby8 HANDLE: 10754/624349
    • [Dataset]
      Roesle, P., Caporaso, L., Schnitte, M., Goldbach, V., Cavallo, L., & Mecking, S. (2015). CCDC 1010351: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc12xbz9. DOI: 10.5517/cc12xbz9 HANDLE: 10754/624350
    ae974a485f413a2113503eed53cd6c53
    10.1021/ja508447d
    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)

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