Selective Reduction of CO2 to CH4 by Tandem Hydrosilylation with Mixed Al/B Catalysts
Type
ArticleKAUST Department
Chemical Science ProgramKAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
Date
2016-04-15Online Publication Date
2016-04-15Print Publication Date
2016-04-27Permanent link to this record
http://hdl.handle.net/10754/604946
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Show full item recordAbstract
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 SocietySponsors
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)PubMed ID
27043820Additional Links
http://pubs.acs.org/doi/abs/10.1021/jacs.6b01497Relations
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
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