Investigation of Surface Alkylation Strategy in SOMC: In Situ Generation of a Silica-Supported Tungsten Methyl Catalyst for Cyclooctane Metathesis

Handle URI:
http://hdl.handle.net/10754/621681
Title:
Investigation of Surface Alkylation Strategy in SOMC: In Situ Generation of a Silica-Supported Tungsten Methyl Catalyst for Cyclooctane Metathesis
Authors:
Hamieh, Ali Imad Ali ( 0000-0002-5218-3617 ) ; Dey, Raju ( 0000-0001-6271-8518 ) ; Samantaray, Manoja; Abdel-Azeim, Safwat ( 0000-0001-8611-1251 ) ; Abou-Hamad, Edy; Chen, Yin; Pelletier, Jeremie ( 0000-0002-4709-4898 ) ; Cavallo, Luigi ( 0000-0002-1398-338X ) ; Basset, Jean-Marie ( 0000-0003-3166-8882 )
Abstract:
An efficient and potentially scalable method is described for the synthesis of the silica-supported complexes [(≡Si-O-)WMe5] and [(≡Si-O-)WMe2(≡CH)] obtained by in situ alkylation of the surface-grafted tungsten chloride [(≡Si-O-)WCl5] (1). [(≡Si-O-)WCl5] can be readily prepared by the reaction of commercially available and stable tungsten hexachloride WCl6 with partially dehydroxylated silica at 700 °C (SiO2-700). Further reaction with ZnMe2 at room temperature rapidly forms a mixture of surface-alkylated tungsten complexes. They were fully characterized by microanalysis, FTIR, mass balance, and solid-state NMR (1H, 13C, 1H-13C HETCOR, 1H-1H double quantum and triple quantum) and identified as [(≡Si-O-)WMe5] and another product, [(≡Si-O-)WMe2(≡CH)]. The latter might have been generated by partial decomposition of the tungsten methyl chloride compound, which is formed during the stepwise alkylation of [(≡Si-O-)WCl5]. DFT calculations were carried out to check the relative stability of the tungsten methyl chloride intermediates and the feasibility of the reaction and corroborate the experimental results. This tungsten complex and its derivative were found to be active catalysts for the metathesis of cyclooctane. © 2016 American Chemical Society.
KAUST Department:
KAUST Catalysis Center (KCC)
Citation:
Hamieh A, Dey R, Samantaray MK, Abdel-Azeim S, Abou-Hamad E, et al. (2016) Investigation of Surface Alkylation Strategy in SOMC: In Situ Generation of a Silica-Supported Tungsten Methyl Catalyst for Cyclooctane Metathesis. Organometallics 35: 2524–2531. Available: http://dx.doi.org/10.1021/acs.organomet.6b00432.
Publisher:
American Chemical Society (ACS)
Journal:
Organometallics
Issue Date:
28-Jul-2016
DOI:
10.1021/acs.organomet.6b00432
Type:
Article
ISSN:
0276-7333; 1520-6041
Sponsors:
This work was supported by the funds from the King Abdullah University of Science and Technology (KAUST).
Appears in Collections:
Articles; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorHamieh, Ali Imad Alien
dc.contributor.authorDey, Rajuen
dc.contributor.authorSamantaray, Manojaen
dc.contributor.authorAbdel-Azeim, Safwaten
dc.contributor.authorAbou-Hamad, Edyen
dc.contributor.authorChen, Yinen
dc.contributor.authorPelletier, Jeremieen
dc.contributor.authorCavallo, Luigien
dc.contributor.authorBasset, Jean-Marieen
dc.date.accessioned2016-11-03T13:22:38Z-
dc.date.available2016-11-03T13:22:38Z-
dc.date.issued2016-07-28en
dc.identifier.citationHamieh A, Dey R, Samantaray MK, Abdel-Azeim S, Abou-Hamad E, et al. (2016) Investigation of Surface Alkylation Strategy in SOMC: In Situ Generation of a Silica-Supported Tungsten Methyl Catalyst for Cyclooctane Metathesis. Organometallics 35: 2524–2531. Available: http://dx.doi.org/10.1021/acs.organomet.6b00432.en
dc.identifier.issn0276-7333en
dc.identifier.issn1520-6041en
dc.identifier.doi10.1021/acs.organomet.6b00432en
dc.identifier.urihttp://hdl.handle.net/10754/621681-
dc.description.abstractAn efficient and potentially scalable method is described for the synthesis of the silica-supported complexes [(≡Si-O-)WMe5] and [(≡Si-O-)WMe2(≡CH)] obtained by in situ alkylation of the surface-grafted tungsten chloride [(≡Si-O-)WCl5] (1). [(≡Si-O-)WCl5] can be readily prepared by the reaction of commercially available and stable tungsten hexachloride WCl6 with partially dehydroxylated silica at 700 °C (SiO2-700). Further reaction with ZnMe2 at room temperature rapidly forms a mixture of surface-alkylated tungsten complexes. They were fully characterized by microanalysis, FTIR, mass balance, and solid-state NMR (1H, 13C, 1H-13C HETCOR, 1H-1H double quantum and triple quantum) and identified as [(≡Si-O-)WMe5] and another product, [(≡Si-O-)WMe2(≡CH)]. The latter might have been generated by partial decomposition of the tungsten methyl chloride compound, which is formed during the stepwise alkylation of [(≡Si-O-)WCl5]. DFT calculations were carried out to check the relative stability of the tungsten methyl chloride intermediates and the feasibility of the reaction and corroborate the experimental results. This tungsten complex and its derivative were found to be active catalysts for the metathesis of cyclooctane. © 2016 American Chemical Society.en
dc.description.sponsorshipThis work was supported by the funds from the King Abdullah University of Science and Technology (KAUST).en
dc.publisherAmerican Chemical Society (ACS)en
dc.titleInvestigation of Surface Alkylation Strategy in SOMC: In Situ Generation of a Silica-Supported Tungsten Methyl Catalyst for Cyclooctane Metathesisen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.identifier.journalOrganometallicsen
kaust.authorHamieh, Ali Imad Alien
kaust.authorDey, Rajuen
kaust.authorSamantaray, Manojaen
kaust.authorAbdel-Azeim, Safwaten
kaust.authorAbou-Hamad, Edyen
kaust.authorChen, Yinen
kaust.authorPelletier, Jeremieen
kaust.authorCavallo, Luigien
kaust.authorBasset, Jean-Marieen
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