Well-Defined Surface Species [(≡Si - O -)W(=O)Me3] Prepared by Direct Methylation of [(≡Si - O -)W(=O)Cl3], a Catalyst for Cycloalkane Metathesis and Transformation of Ethylene to Propylene

Handle URI:
http://hdl.handle.net/10754/564137
Title:
Well-Defined Surface Species [(≡Si - O -)W(=O)Me3] Prepared by Direct Methylation of [(≡Si - O -)W(=O)Cl3], a Catalyst for Cycloalkane Metathesis and Transformation of Ethylene to Propylene
Authors:
Hamieh, Ali Imad Ali ( 0000-0002-5218-3617 ) ; Chen, Yin; Abdel-Azeim, Safwat ( 0000-0001-8611-1251 ) ; Abou-Hamad, Edy; Goh, Li Min Serena; Samantaray, Manoja; Dey, Raju ( 0000-0001-6271-8518 ) ; Cavallo, Luigi ( 0000-0002-1398-338X ) ; Basset, Jean-Marie ( 0000-0003-3166-8882 )
Abstract:
The silica-supported tungsten oxo-trimethyl complex [(≡Si - O -)W(=O)Me3] was synthesized using a novel SOMC synthetic approach. By grafting the inexpensive stable compound WOCl4 on the surface of silica, partially dehydroxylated at 700 °C (SiO2-700), a well-defined monopodal surface complex [(≡Si - O -)W(=O)Cl3] was produced. The supported complex directly methylated with ZnMe2 and transformed into [(≡Si - O -)W(=O)Me3], which we fully characterized by microanalysis, IR, mass balance and SS NMR (1H, 13C, 1H-13C HETCOR, 1H-1H DQ and TQ). [(≡Si - O)W(=O)Me3] has two conformational isomers on the surface at room temperature. The conversion of one to the other was observed at 318 K by variable-temperature 13C CP/MAS and 1H spin echo MAS solid-state NMR; this was also confirmed by NMR and DFT calculations. [(≡Si - O)W(=O)Me3] was found to be active in cyclooctane metathesis and to have a wide distribution range in ring-contracted and ring-expanded products. In addition, [(≡Si - O)W(=O)Me3] proved to be highly active for selective transformation of ethylene to propylene compared to other silica-supported organometallic complexes. (Chemical Equation Presented). © 2015 American Chemical Society.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division; Chemical Science Program; Solar and Photovoltaic Engineering Research Center (SPERC)
Publisher:
American Chemical Society (ACS)
Journal:
ACS Catalysis
Issue Date:
3-Apr-2015
DOI:
10.1021/cs5020749
Type:
Article
ISSN:
21555435
Sponsors:
This work was supported by funds from King Abdullah University of Science and Technology (KAUST).
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC); Solar and Photovoltaic Engineering Research Center (SPERC)

Full metadata record

DC FieldValue Language
dc.contributor.authorHamieh, Ali Imad Alien
dc.contributor.authorChen, Yinen
dc.contributor.authorAbdel-Azeim, Safwaten
dc.contributor.authorAbou-Hamad, Edyen
dc.contributor.authorGoh, Li Min Serenaen
dc.contributor.authorSamantaray, Manojaen
dc.contributor.authorDey, Rajuen
dc.contributor.authorCavallo, Luigien
dc.contributor.authorBasset, Jean-Marieen
dc.date.accessioned2015-08-03T12:33:44Zen
dc.date.available2015-08-03T12:33:44Zen
dc.date.issued2015-04-03en
dc.identifier.issn21555435en
dc.identifier.doi10.1021/cs5020749en
dc.identifier.urihttp://hdl.handle.net/10754/564137en
dc.description.abstractThe silica-supported tungsten oxo-trimethyl complex [(≡Si - O -)W(=O)Me3] was synthesized using a novel SOMC synthetic approach. By grafting the inexpensive stable compound WOCl4 on the surface of silica, partially dehydroxylated at 700 °C (SiO2-700), a well-defined monopodal surface complex [(≡Si - O -)W(=O)Cl3] was produced. The supported complex directly methylated with ZnMe2 and transformed into [(≡Si - O -)W(=O)Me3], which we fully characterized by microanalysis, IR, mass balance and SS NMR (1H, 13C, 1H-13C HETCOR, 1H-1H DQ and TQ). [(≡Si - O)W(=O)Me3] has two conformational isomers on the surface at room temperature. The conversion of one to the other was observed at 318 K by variable-temperature 13C CP/MAS and 1H spin echo MAS solid-state NMR; this was also confirmed by NMR and DFT calculations. [(≡Si - O)W(=O)Me3] was found to be active in cyclooctane metathesis and to have a wide distribution range in ring-contracted and ring-expanded products. In addition, [(≡Si - O)W(=O)Me3] proved to be highly active for selective transformation of ethylene to propylene compared to other silica-supported organometallic complexes. (Chemical Equation Presented). © 2015 American Chemical Society.en
dc.description.sponsorshipThis work was supported by funds from King Abdullah University of Science and Technology (KAUST).en
dc.publisherAmerican Chemical Society (ACS)en
dc.subjectcyclooctane metathesisen
dc.subjectethylene propylene conversionen
dc.subjectsurface methylationen
dc.subjectsurface organometallic chemistryen
dc.subjecttungsten oxo compounden
dc.titleWell-Defined Surface Species [(≡Si - O -)W(=O)Me3] Prepared by Direct Methylation of [(≡Si - O -)W(=O)Cl3], a Catalyst for Cycloalkane Metathesis and Transformation of Ethylene to Propyleneen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentChemical Science Programen
dc.contributor.departmentSolar and Photovoltaic Engineering Research Center (SPERC)en
dc.identifier.journalACS Catalysisen
kaust.authorChen, Yinen
kaust.authorAbdel-Azeim, Safwaten
kaust.authorAbou-Hamad, Edyen
kaust.authorSamantaray, Manojaen
kaust.authorDey, Rajuen
kaust.authorCavallo, Luigien
kaust.authorBasset, Jean-Marieen
kaust.authorHamieh, Ali Imad Alien
kaust.authorGoh, Li Min Serenaen
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