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dc.contributor.authorPump, Eva
dc.contributor.authorCao, Zhen
dc.contributor.authorSamantaray, Manoja
dc.contributor.authorBendjeriou-Sedjerari, Anissa
dc.contributor.authorCavallo, Luigi
dc.contributor.authorBasset, Jean-Marie
dc.date.accessioned2017-08-29T14:04:24Z
dc.date.available2017-08-29T14:04:24Z
dc.date.issued2017-08-31
dc.identifier.citationPump E, Cao Z, Samantaray MK, Bendjeriou-Sedjerari A, Cavallo L, et al. (2017) Exploiting Confinement Effects to Tune Selectivity in Cyclooctane Metathesis. ACS Catalysis. Available: http://dx.doi.org/10.1021/acscatal.7b01249.
dc.identifier.issn2155-5435
dc.identifier.issn2155-5435
dc.identifier.doi10.1021/acscatal.7b01249
dc.identifier.urihttp://hdl.handle.net/10754/625417
dc.description.abstractThe mechanism of cyclooctane metathesis using confinement effect strategies in mesoporous silica nanoparticles (MSNs) is discussed by catalytic experiments and density functional theory (DFT) calculations. WMe6 was immobilized inside the pores of a series of MSNs having the same structure but different pore diameters (60, 30 and 25 Å). Experiments in cyclooctane metathesis suggest that confinement effects observed in smaller pores (30 and 25 Å) improve selectivity towards the dimeric cyclohexadecane. In contrast, in larger pores (60 Å) a broad product distribution dominated by ring contracted cycloalkanes was found. The catalytic cycle and potential side reactions occurring at [(≡SiO-)WMe5] were examined with DFT calculations. Analysis of the geometries for the key reaction intermediates allowed to rationalize the impact of a confined environment on the enhanced selectivity towards the dimeric product in smaller pores, while in large pores the ring contracted products are favored.
dc.description.sponsorshipThe research reported in this publication was supported by funding from the King Abdullah University of Science and Technology (KAUST). The authors are grateful to the KAUST Supercomputing Laboratory (KSL) for the resources provided.
dc.publisherAmerican Chemical Society (ACS)
dc.relation.urlhttp://pubs.acs.org/doi/10.1021/acscatal.7b01249
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Catalysis, 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/10.1021/acscatal.7b01249.
dc.titleExploiting Confinement Effects to Tune Selectivity in Cyclooctane Metathesis
dc.typeArticle
dc.contributor.departmentChemical Science Program
dc.contributor.departmentKAUST Catalysis Center (KCC)
dc.contributor.departmentPhysical Science and Engineering (PSE) Division
dc.identifier.journalACS Catalysis
dc.eprint.versionPost-print
kaust.personPump, Eva
kaust.personCao, Zhen
kaust.personSamantaray, Manoja
kaust.personBendjeriou-Sedjerari, Anissa
kaust.personCavallo, Luigi
kaust.personBasset, Jean-Marie
refterms.dateFOA2018-08-24T00:00:00Z
dc.date.published-online2017-08-31
dc.date.published-print2017-10-06


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