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    Selective Reduction of CO2 to CH4 by Tandem Hydrosilylation with Mixed Al/B Catalysts

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    Type
    Article
    Authors
    Chen, Jiawei
    Falivene, Laura cc
    Caporaso, Lucia cc
    Cavallo, Luigi cc
    Chen, Eugene Y.-X. cc
    KAUST Department
    Chemical Science Program
    KAUST Catalysis Center (KCC)
    Physical Science and Engineering (PSE) Division
    Date
    2016-04-15
    Online Publication Date
    2016-04-15
    Print Publication Date
    2016-04-27
    Permanent link to this record
    http://hdl.handle.net/10754/604946
    
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    Abstract
    This contribution reports the first example of highly selective reduction of CO2 into CH4 via tandem hydrosilylation with mixed main-group organo-Lewis acid (LA) catalysts [Al(C6F5)3 + B(C6F5)3] {[Al] + [B]}. As shown by this comprehensive experimental and computational study, in this unique tandem catalytic process, [Al] effectively mediates the first step of the overall reduction cycle, namely the fixation of CO2 into HCOOSiEt3 (1) via the LA-mediated C=O activation, while [B] is incapable of promoting the same transformation. On the other hand, [B] is shown to be an excellent catalyst for the subsequent reduction steps 2–4, namely the hydrosilylation of the more basic intermediates [1 to H2C(OSiEt3)2 (2) to H3COSiEt3 (3) and finally to CH4] through the frustrated-Lewis-pair (FLP)-type Si–H activation. Hence, with the required combination of [Al] and [B], a highly selective hydrosilylative reduction of CO2 system has been developed, achieving high CH4 production yield up to 94%. The remarkably different catalytic behaviors between [Al] and [B] are attributed to the higher overall Lewis acidity of [Al] derived from two conflicting factors (electronic and steric effects), which renders the higher tendency of [Al] to form stable [Al]–substrate (intermediate) adducts with CO2 as well as subsequent intermediates 1, 2 and 3. Overall, the roles of [Al] and [B] are not only complementary but also synergistic in the total reduction of CO2, which render both [Al]-mediated first reduction step and [B]-mediated subsequent steps catalytic.
    Citation
    Selective Reduction of CO2 to CH4 by Tandem Hydrosilylation with Mixed Al/B Catalysts 2016 Journal of the American Chemical Society
    Sponsors
    This work was supported by the US National Science Foundation (NSF- CHE- 1507702) for the study carried out at Colorado State University and by the funding from King Abdullah University of Science and Technology (KAUST) for the study performed at KAUST. We thank Boulder Scientific Co. for the research gift of B(C6F5)3.
    Publisher
    American Chemical Society (ACS)
    Journal
    Journal of the American Chemical Society
    DOI
    10.1021/jacs.6b01497
    PubMed ID
    27043820
    Additional Links
    http://pubs.acs.org/doi/abs/10.1021/jacs.6b01497
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    Is Supplemented By:
    • [Dataset]
      Chen, J., Falivene, L., Caporaso, L., Cavallo, L., & Chen, E. Y.-X. (2016). CCDC 1446069: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc1kjrd7. DOI: 10.5517/ccdc.csd.cc1kjrd7 HANDLE: 10754/624555
    • [Dataset]
      Chen, J., Falivene, L., Caporaso, L., Cavallo, L., & Chen, E. Y.-X. (2016). CCDC 1446070: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc1kjrf8. DOI: 10.5517/ccdc.csd.cc1kjrf8 HANDLE: 10754/624556
    ae974a485f413a2113503eed53cd6c53
    10.1021/jacs.6b01497
    Scopus Count
    Collections
    Articles; Physical Science and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

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