Tungsten Catalyst Incorporating a Well-Defined Tetracoordinated Aluminum Surface Ligand for Selective Metathesis of Propane, [(≡Si−O−Si≡)(≡Si−O−)2 Al−O−W(≡Ct Bu) (H)2 ]
Morlanes, Natalia Sanchez
Bhatte, Kushal Deepak
Gates, Bruce C.
KAUST DepartmentPhysical Sciences and Engineering (PSE) Division
Chemical Science Program
KAUST Catalysis Center (KCC)
Imaging and Characterization Core Lab
University of Science and Technology 4700 King Abdullah; Thuwal 23955-6900 Kingdom of Saudi Arabia
King Abdullah University of Science and Technology ( KAUST) Core Labs; Thuwal 23955-6900 Kingdom of Saudi Arabia
Permanent link to this recordhttp://hdl.handle.net/10754/631591
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AbstractA well-defined aluminium-bound hydroxyl group on the surface of mesoporous SBA-15, [(≡Si−O−Si≡) (≡Si−O) 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) Al (isobutyl) fragment undergoes β-H elimination at 400 °C leading to [(≡Si−O−Si≡)(≡Si−O−)Al−O) Al−H]. Further oxidation of this Al-hydride with NO leads to 3. This acidic support was used to create a well-defined surface organo-tungsten fragment [(≡Si−O−Si≡)(≡Si−O−)Al−O−W(≡CtBu)(CHtBu)] by reacting 3 with W(≡C-tBu)(CH-tBu). A further reaction with hydrogen under mild conditions afforded the tungsten carbyne bis-hydride [(≡Si−O−Si≡)(≡Si−O−)Al−O−W(H)(≡C-tBu)]. 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−) Al−O−W(≡CtBu)(H)] 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.
CitationWerghi B, Bendjeriou-Sedjerari A, Jedidi A, Morlanes N, Abou-Hamad E, et al. (2018) Tungsten Catalyst Incorporating a Well-Defined Tetracoordinated Aluminum Surface Ligand for Selective Metathesis of Propane, [(≡Si−O−Si≡)(≡Si−O−)2 Al−O−W(≡Ct Bu) (H)2 ]. ChemCatChem 11: 614–620. Available: http://dx.doi.org/10.1002/cctc.201801779.
SponsorsThe research was supported by the King Abdullah University of Science and Technology and by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Grant DE-FG02-04ER15513. We acknowledge the European Synchrotron Radiation Facility for providing synchrotron radiation facilities. L.C. and A. J. are grateful to the KAUST Supercomputing Laboratory for the resources. A. J. thank High-Performance Computing Center (AZIZ supercomputer) for the support.