Unearthing a Well-Defined Highly Active Bimetallic W/Ti Precatalyst Anchored on a Single Silica Surface for Metathesis of Propane

Handle URI:
http://hdl.handle.net/10754/623929
Title:
Unearthing a Well-Defined Highly Active Bimetallic W/Ti Precatalyst Anchored on a Single Silica Surface for Metathesis of Propane
Authors:
Samantaray, Manoja; Kavitake, Santosh Giridhar; Morlanes, Natalia Sanchez ( 0000-0002-5356-9255 ) ; Abou-Hamad, Edy; Hamieh, Ali Imad Ali ( 0000-0002-5218-3617 ) ; Dey, Raju ( 0000-0001-6271-8518 ) ; Basset, Jean-Marie ( 0000-0003-3166-8882 )
Abstract:
Two compatible organometallic complexes, W(Me)(6) (1) and TiNp4 (2), were successively anchored on a highly dehydroxylated single silica support (SiO2-700) to synthesize the well-defined bimetallic precatalyst [(equivalent to Si-O-)W(Me)(5)(equivalent to Si-O-)Ti(Np)(3)] (4). Precatalyst 4 was characterized at the molecular level using advanced surface organometallic chemistry (SOMC) characterization techniques. The strong autocorrelation observed between methyl of W and Ti in H-1-H-1 multiple-quantum NMR spectra demonstrates that W and Ti species are in close proximity to each other. The bimetallic precatalyst 4, with a turnover number (TON) of 9784, proved to be significantly more efficient than the silica-supported monometallic catalyst [(equivalent to Si-O-)W(Me)(5)] (3), with a TON of 98, for propane metathesis at 150 degrees C in a flow reactor. The dramatic improvement in the activity signifies the cooperativity between Ti and W and indicates that the key step of alkane metathesis (C-H bond activation followed by beta-H elimination) occurs on Ti, followed by olefin metathesis, which occurs on W. We have demonstrated the influence and importance of proximity of Ti to W for achieving such a significantly high activity. This is the first report demonstrating the considerably high activity (TON = 9784) in propane metathesis at moderate temperature (150 degrees C) using a well-defined bimetallic system prepared via the SOMC approach.
KAUST Department:
KAUST Catalysis Center (KCC)
Citation:
Samantaray MK, Kavitake S, Morlanés N, Abou-Hamad E, Hamieh A, et al. (2017) Unearthing a Well-Defined Highly Active Bimetallic W/Ti Precatalyst Anchored on a Single Silica Surface for Metathesis of Propane. Journal of the American Chemical Society 139: 3522–3527. Available: http://dx.doi.org/10.1021/jacs.6b12970.
Publisher:
American Chemical Society (ACS)
Journal:
Journal of the American Chemical Society
Issue Date:
10-Feb-2017
DOI:
10.1021/jacs.6b12970
Type:
Article
ISSN:
0002-7863; 1520-5126
Sponsors:
The authors acknowledge the KAUST Nuclear Magnetic Resonance Core Lab and Analytical Core Lab (ACL) for the analysis of the sample. This publication is based upon work supported by the King Abdullah University of Science and Technology (KAUST) Office of Sponsored Research (OSR).
Additional Links:
http://pubs.acs.org/doi/abs/10.1021/jacs.6b12970
Appears in Collections:
Articles; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorSamantaray, Manojaen
dc.contributor.authorKavitake, Santosh Giridharen
dc.contributor.authorMorlanes, Natalia Sanchezen
dc.contributor.authorAbou-Hamad, Edyen
dc.contributor.authorHamieh, Ali Imad Alien
dc.contributor.authorDey, Rajuen
dc.contributor.authorBasset, Jean-Marieen
dc.date.accessioned2017-05-31T11:23:14Z-
dc.date.available2017-05-31T11:23:14Z-
dc.date.issued2017-02-10en
dc.identifier.citationSamantaray MK, Kavitake S, Morlanés N, Abou-Hamad E, Hamieh A, et al. (2017) Unearthing a Well-Defined Highly Active Bimetallic W/Ti Precatalyst Anchored on a Single Silica Surface for Metathesis of Propane. Journal of the American Chemical Society 139: 3522–3527. Available: http://dx.doi.org/10.1021/jacs.6b12970.en
dc.identifier.issn0002-7863en
dc.identifier.issn1520-5126en
dc.identifier.doi10.1021/jacs.6b12970en
dc.identifier.urihttp://hdl.handle.net/10754/623929-
dc.description.abstractTwo compatible organometallic complexes, W(Me)(6) (1) and TiNp4 (2), were successively anchored on a highly dehydroxylated single silica support (SiO2-700) to synthesize the well-defined bimetallic precatalyst [(equivalent to Si-O-)W(Me)(5)(equivalent to Si-O-)Ti(Np)(3)] (4). Precatalyst 4 was characterized at the molecular level using advanced surface organometallic chemistry (SOMC) characterization techniques. The strong autocorrelation observed between methyl of W and Ti in H-1-H-1 multiple-quantum NMR spectra demonstrates that W and Ti species are in close proximity to each other. The bimetallic precatalyst 4, with a turnover number (TON) of 9784, proved to be significantly more efficient than the silica-supported monometallic catalyst [(equivalent to Si-O-)W(Me)(5)] (3), with a TON of 98, for propane metathesis at 150 degrees C in a flow reactor. The dramatic improvement in the activity signifies the cooperativity between Ti and W and indicates that the key step of alkane metathesis (C-H bond activation followed by beta-H elimination) occurs on Ti, followed by olefin metathesis, which occurs on W. We have demonstrated the influence and importance of proximity of Ti to W for achieving such a significantly high activity. This is the first report demonstrating the considerably high activity (TON = 9784) in propane metathesis at moderate temperature (150 degrees C) using a well-defined bimetallic system prepared via the SOMC approach.en
dc.description.sponsorshipThe authors acknowledge the KAUST Nuclear Magnetic Resonance Core Lab and Analytical Core Lab (ACL) for the analysis of the sample. This publication is based upon work supported by the King Abdullah University of Science and Technology (KAUST) Office of Sponsored Research (OSR).en
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/abs/10.1021/jacs.6b12970en
dc.titleUnearthing a Well-Defined Highly Active Bimetallic W/Ti Precatalyst Anchored on a Single Silica Surface for Metathesis of Propaneen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.identifier.journalJournal of the American Chemical Societyen
kaust.authorSamantaray, Manojaen
kaust.authorKavitake, Santosh Giridharen
kaust.authorMorlanes, Natalia Sanchezen
kaust.authorAbou-Hamad, Edyen
kaust.authorHamieh, Ali Imad Alien
kaust.authorDey, Rajuen
kaust.authorBasset, Jean-Marieen
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