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dc.contributor.authorChen, Jiawei
dc.contributor.authorFalivene, Laura
dc.contributor.authorCaporaso, Lucia
dc.contributor.authorCavallo, Luigi
dc.contributor.authorChen, Eugene Y.-X.
dc.date.accessioned2016-04-10T13:42:39Z
dc.date.available2016-04-10T13:42:39Z
dc.date.issued2016-04-15
dc.identifier.citationSelective Reduction of CO2 to CH4 by Tandem Hydrosilylation with Mixed Al/B Catalysts 2016 Journal of the American Chemical Society
dc.identifier.issn0002-7863
dc.identifier.issn1520-5126
dc.identifier.pmid27043820
dc.identifier.doi10.1021/jacs.6b01497
dc.identifier.urihttp://hdl.handle.net/10754/604946
dc.description.abstractThis 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.
dc.description.sponsorshipThis 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.
dc.language.isoen
dc.publisherAmerican Chemical Society (ACS)
dc.relation.urlhttp://pubs.acs.org/doi/abs/10.1021/jacs.6b01497
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/jacs.6b01497.
dc.titleSelective Reduction of CO2 to CH4 by Tandem Hydrosilylation with Mixed Al/B Catalysts
dc.typeArticle
dc.contributor.departmentChemical Science Program
dc.contributor.departmentKAUST Catalysis Center (KCC)
dc.contributor.departmentPhysical Science and Engineering (PSE) Division
dc.identifier.journalJournal of the American Chemical Society
dc.eprint.versionPost-print
dc.contributor.institutionDepartment of Chemistry, Colorado State University, Fort Collins, Colorado 80523-1872, USA
dc.contributor.institutionDipartimento di Chimica e Biologia, Università di Salerno, Via Papa Paolo Giovanni II, I-84084, Fisciano, Italy
dc.contributor.affiliationKing Abdullah University of Science and Technology (KAUST)
kaust.personFalivene, Laura
kaust.personCavallo, Luigi
dc.relation.issupplementedbyDOI:10.5517/ccdc.csd.cc1kjrd7
dc.relation.issupplementedbyDOI:10.5517/ccdc.csd.cc1kjrf8
refterms.dateFOA2017-04-04T00:00:00Z
display.relations<b> Is Supplemented By:</b> <br/> <ul><li><i>[Dataset]</i> <br/> 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: <a href="https://doi.org/10.5517/ccdc.csd.cc1kjrd7">10.5517/ccdc.csd.cc1kjrd7</a> HANDLE: <a href="http://hdl.handle.net/10754/624555">10754/624555</a></li><li><i>[Dataset]</i> <br/> 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: <a href="https://doi.org/10.5517/ccdc.csd.cc1kjrf8">10.5517/ccdc.csd.cc1kjrf8</a> HANDLE: <a href="http://hdl.handle.net/10754/624556">10754/624556</a></li></ul>
dc.date.published-online2016-04-15
dc.date.published-print2016-04-27


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