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Title: Tungsten Catalyst Incorporating a Well‐Defined Tetracoordinated Aluminum Surface Ligand for Selective Metathesis of Propane, [(≡Si−O−Si≡)(≡Si−O−) 2 Al−O−W(≡C t Bu) (H) 2 ]

Abstract

Abstract A well‐defined aluminium‐bound hydroxyl group on the surface of mesoporous SBA‐15, [(≡Si−O−Si≡) (≡Si−O) 2 Al−OH], 3 was obtained by reacting di‐isopropyl aluminium hydride with SBA‐15 treated at 700 °C. The resulting surface [(≡Si−O−Si≡) (≡Si−O) 2 Al (isobutyl) fragment undergoes β‐H elimination at 400 °C leading to [(≡Si−O−Si≡)(≡Si−O−) 2 Al−O) Al−H]. Further oxidation of this Al‐hydride with N 2 O leads to 3 . This acidic support was used to create a well‐defined surface organo‐tungsten fragment [(≡Si−O−Si≡)(≡Si−O−) 2 Al−O−W(≡C t Bu)(CH 2 tBu) 2 ] by reacting 3 with W(≡C‐ t Bu)(CH 2 ‐ t Bu) 3 . A further reaction with hydrogen under mild conditions afforded the tungsten carbyne bis‐hydride [(≡Si−O−Si≡)(≡Si−O−) 2 Al−O−W(H) 2 (≡C‐ t Bu)]. The performance of each of the W‐supported catalysts was assessed for propane metathesis in a flow reactor at 150 °C. [(≡Si−O−Si≡)(≡Si−O−) 2 Al−O−W(≡C t Bu)(H) 2 ] was found to be a single‐site catalyst, giving the highest turnover number (TON=800) and the highest reported selectivity for butane (45 %) vs . ethane (32 %) known for oxide‐supported tungsten complex catalysts (with the supports being silica, silica‐alumina, and alumina). The results demonstrate that modification of the oxide ligands on silica via the creation of Al Lewis acid centermore » as an anchoring site for organometallic complexes opens up new catalytic properties, markedly enhancing the catalytic performance of supported organo‐tungsten species.« less

Authors:
 [1];  [1];  [2];  [1];  [3];  [1];  [4];  [5];  [6];  [1];  [1];  [5]; ORCiD logo [1]
+ Show Author Affiliations
  1. University of Science and Technology 4700 King Abdullah Thuwal 23955-6900 Kingdom of Saudi Arabia
  2. Department of Chemistry Faculty of Science King Abdulaziz University (KAU) Jeddah 21589 Kingdom of Saudi Arabia
  3. King Abdullah University of Science and Technology(KAUST) Core Labs Thuwal 23955-6900 Kingdom of Saudi Arabia
  4. Department of Materials Science and Engineering University of California Davis CA 95616 USA
  5. Department of Chemical Engineering University of California Davis CA 95616 USA
  6. Institut Néel UPR 2940 CNRS Université Grenoble Alpes Grenoble F-38000 France
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1488689
Resource Type:
Publisher's Accepted Manuscript
Journal Name:
ChemCatChem
Additional Journal Information:
Journal Name: ChemCatChem Journal Volume: 11 Journal Issue: 1; Journal ID: ISSN 1867-3880
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Werghi, Baraa, Bendjeriou‐Sedjerari, Anissa, Jedidi, Abdesslem, Morlanes, Natalia, Abou‐Hamad, Edy, Bhatte, Kushal, Guan, Erjia, Ma, Tao, Aguilar‐Tapia, Antonio, Ould‐Chikh, Samy, Cavallo, Luigi, Gates, Bruce C., and Basset, Jean‐Marie. Tungsten Catalyst Incorporating a Well‐Defined Tetracoordinated Aluminum Surface Ligand for Selective Metathesis of Propane, [(≡Si−O−Si≡)(≡Si−O−) 2 Al−O−W(≡C t Bu) (H) 2 ]. Germany: N. p., 2018. Web. doi:10.1002/cctc.201801779.
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Werghi, Baraa, Bendjeriou‐Sedjerari, Anissa, Jedidi, Abdesslem, Morlanes, Natalia, Abou‐Hamad, Edy, Bhatte, Kushal, Guan, Erjia, Ma, Tao, Aguilar‐Tapia, Antonio, Ould‐Chikh, Samy, Cavallo, Luigi, Gates, Bruce C., & Basset, Jean‐Marie. Tungsten Catalyst Incorporating a Well‐Defined Tetracoordinated Aluminum Surface Ligand for Selective Metathesis of Propane, [(≡Si−O−Si≡)(≡Si−O−) 2 Al−O−W(≡C t Bu) (H) 2 ]. Germany. https://doi.org/10.1002/cctc.201801779
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Werghi, Baraa, Bendjeriou‐Sedjerari, Anissa, Jedidi, Abdesslem, Morlanes, Natalia, Abou‐Hamad, Edy, Bhatte, Kushal, Guan, Erjia, Ma, Tao, Aguilar‐Tapia, Antonio, Ould‐Chikh, Samy, Cavallo, Luigi, Gates, Bruce C., and Basset, Jean‐Marie. Fri . "Tungsten Catalyst Incorporating a Well‐Defined Tetracoordinated Aluminum Surface Ligand for Selective Metathesis of Propane, [(≡Si−O−Si≡)(≡Si−O−) 2 Al−O−W(≡C t Bu) (H) 2 ]". Germany. https://doi.org/10.1002/cctc.201801779.
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@article{osti_1488689,
title = {Tungsten Catalyst Incorporating a Well‐Defined Tetracoordinated Aluminum Surface Ligand for Selective Metathesis of Propane, [(≡Si−O−Si≡)(≡Si−O−) 2 Al−O−W(≡C t Bu) (H) 2 ]},
author = {Werghi, Baraa and Bendjeriou‐Sedjerari, Anissa and Jedidi, Abdesslem and Morlanes, Natalia and Abou‐Hamad, Edy and Bhatte, Kushal and Guan, Erjia and Ma, Tao and Aguilar‐Tapia, Antonio and Ould‐Chikh, Samy and Cavallo, Luigi and Gates, Bruce C. and Basset, Jean‐Marie},
abstractNote = {Abstract A well‐defined aluminium‐bound hydroxyl group on the surface of mesoporous SBA‐15, [(≡Si−O−Si≡) (≡Si−O) 2 Al−OH], 3 was obtained by reacting di‐isopropyl aluminium hydride with SBA‐15 treated at 700 °C. The resulting surface [(≡Si−O−Si≡) (≡Si−O) 2 Al (isobutyl) fragment undergoes β‐H elimination at 400 °C leading to [(≡Si−O−Si≡)(≡Si−O−) 2 Al−O) Al−H]. Further oxidation of this Al‐hydride with N 2 O leads to 3 . This acidic support was used to create a well‐defined surface organo‐tungsten fragment [(≡Si−O−Si≡)(≡Si−O−) 2 Al−O−W(≡C t Bu)(CH 2 tBu) 2 ] by reacting 3 with W(≡C‐ t Bu)(CH 2 ‐ t Bu) 3 . A further reaction with hydrogen under mild conditions afforded the tungsten carbyne bis‐hydride [(≡Si−O−Si≡)(≡Si−O−) 2 Al−O−W(H) 2 (≡C‐ t Bu)]. The performance of each of the W‐supported catalysts was assessed for propane metathesis in a flow reactor at 150 °C. [(≡Si−O−Si≡)(≡Si−O−) 2 Al−O−W(≡C t Bu)(H) 2 ] was found to be a single‐site catalyst, giving the highest turnover number (TON=800) and the highest reported selectivity for butane (45 %) vs . ethane (32 %) known for oxide‐supported tungsten complex catalysts (with the supports being silica, silica‐alumina, and alumina). The results demonstrate that modification of the oxide ligands on silica via the creation of Al Lewis acid center as an anchoring site for organometallic complexes opens up new catalytic properties, markedly enhancing the catalytic performance of supported organo‐tungsten species.},
doi = {10.1002/cctc.201801779},
journal = {ChemCatChem},
number = 1,
volume = 11,
place = {Germany},
year = {Fri Dec 21 00:00:00 EST 2018},
month = {Fri Dec 21 00:00:00 EST 2018}
}
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https://doi.org/10.1002/cctc.201801779
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