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    Tailored strength neighboring group interactions switch polymerization to dimerization catalysis

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    Type
    Article
    Authors
    Schiebel, Eva
    Santacroce, Stefano
    Falivene, Laura cc
    Göttker-Schnetmann, Inigo
    Caporaso, Lucia
    Mecking, Stefan
    KAUST Department
    KAUST Catalysis Center (KCC)
    Physical Science and Engineering (PSE) Division
    Date
    2019-03-21
    Online Publication Date
    2019-03-21
    Print Publication Date
    2019-05-03
    Permanent link to this record
    http://hdl.handle.net/10754/631774
    
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    Abstract
    A combined experimental and theoretical study elucidates how Ni∙∙∙O neighboring group interactions drastically switch catalytic properties towards ethylene. A range of salicylaldiminato complexes with aryloxy groups in 2,6-position of the N-phenyl group were found to dimerize and oligomerize ethylene to butenes and branched oligomers (C4, C6, C8, C10…) in pressure reactor experiments, while corresponding reference catalysts with arylmethylene groups yield linear polyethylene with Mn 100.000 g mol-1. While both types of catalysts consume ethylene with similar high activities (105 turnovers h-1), the rate of ß-hydride elimination (BHE) is much increased for the case of aryloxy substitution. DFT studies show that formation of the relevant cis-agostic complex from which BHE occurs by displacement of ethylene from the cis-alkyl olefin complex is promoted by an Ni∙∙∙O interaction. This low energy pathway renders chain transfer competitive with insertion chain growth. The resulting Ni∙∙∙O intermediate is rather stable and similar in energy to key species of catalysis (ß-agostic and alkyl olefin complexes) but barely not yet an energetic sink that would impede catalysis.
    Citation
    Schiebel E, Santacroce S, Falivene L, Göttker-Schnetmann I, Caporaso L, et al. (2019) Tailored strength neighboring group interactions switch polymerization to dimerization catalysis. ACS Catalysis. Available: http://dx.doi.org/10.1021/acscatal.9b00129.
    Sponsors
    Financial support by the DFG (Me 1388/14-1) is gratefully acknowledged. We thank Steffen Oßwald for assistance with the CV measurements and Lars Bolk for DSC and GPC measurements.
    Publisher
    American Chemical Society (ACS)
    Journal
    ACS Catalysis
    DOI
    10.1021/acscatal.9b00129
    Additional Links
    https://pubs.acs.org/doi/10.1021/acscatal.9b00129
    Relations
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    ae974a485f413a2113503eed53cd6c53
    10.1021/acscatal.9b00129
    Scopus Count
    Collections
    Articles; Physical Science and Engineering (PSE) Division; KAUST Catalysis Center (KCC)

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