Exploiting Confinement Effects to Tune Selectivity in Cyclooctane Metathesis

Handle URI:
http://hdl.handle.net/10754/625417
Title:
Exploiting Confinement Effects to Tune Selectivity in Cyclooctane Metathesis
Authors:
Pump, Eva ( 0000-0003-2810-2546 ) ; Cao, Zhen; Samantaray, Manoja K; Bendjeriou-Sedjerari, Anissa; Cavallo, Luigi ( 0000-0002-1398-338X ) ; Basset, Jean-Marie ( 0000-0003-3166-8882 )
Abstract:
The 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.
KAUST Department:
KAUST Catalysis Center (KCC)
Citation:
Pump 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.
Publisher:
American Chemical Society (ACS)
Journal:
ACS Catalysis
Issue Date:
24-Aug-2017
DOI:
10.1021/acscatal.7b01249
Type:
Article
ISSN:
2155-5435; 2155-5435
Sponsors:
The 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.
Additional Links:
http://pubs.acs.org/doi/10.1021/acscatal.7b01249
Appears in Collections:
Articles; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorPump, Evaen
dc.contributor.authorCao, Zhenen
dc.contributor.authorSamantaray, Manoja Ken
dc.contributor.authorBendjeriou-Sedjerari, Anissaen
dc.contributor.authorCavallo, Luigien
dc.contributor.authorBasset, Jean-Marieen
dc.date.accessioned2017-08-29T14:04:24Z-
dc.date.available2017-08-29T14:04:24Z-
dc.date.issued2017-08-24en
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.en
dc.identifier.issn2155-5435en
dc.identifier.issn2155-5435en
dc.identifier.doi10.1021/acscatal.7b01249en
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.en
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.en
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/10.1021/acscatal.7b01249en
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.en
dc.titleExploiting Confinement Effects to Tune Selectivity in Cyclooctane Metathesisen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.identifier.journalACS Catalysisen
dc.eprint.versionPost-printen
kaust.authorPump, Evaen
kaust.authorCao, Zhenen
kaust.authorSamantaray, Manoja Ken
kaust.authorBendjeriou-Sedjerari, Anissaen
kaust.authorCavallo, Luigien
kaust.authorBasset, Jean-Marieen
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