ACS Catalysis
Research Article
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glovebox where cyclooctane (0.5 mL, 3.7 mmol) was added.
The ampule was sealed under vacuum pressure, immersed in an
oil bath, and heated at 150 °C for 7 days. At the end of the
reaction, the ampule was cooled using liquid nitrogen. The
mixture was quenched by adding a fixed amount of dichloro-
methane after filtration; the resulting solution was analyzed by
GC and GC-MS.
Ethylene to Propylene Using [(Si−O−)W(O)Me3]. One
hundred milligrams of complex 3 was placed in a 300 mL batch
reactor, and after evacuation to 10−5 mbar, 0.95 atm of dry
ethylene was introduced (substrate/catalyst ratio around 500).
The reactor was heated at 150 °C for 18 h. The final products
were analyzed by GC.
DFT Computational Details. All quantum chemical
computations were performed using the Amsterdam Density
Functional (ADF)28 and Gaussian 09 programs. NMR
calculations were made for each of the two different
conformations depicted in Figure 6. The two different models
represent the position of the oxygen atoms around tungsten; in
the first conformation (A) the oxygen atom is perpendicular to
the plane of the three methyl groups. In the second
conformation (B) the position of the oxygen atom exchanged
with one methyl group.
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First, geometry optimizations were performed using
Gaussian 09 with the generalized gradient approximation
(GGA) exchange-correlation function developed by Perdew,
Burke, and Ernzerhof (PBE)29,30 an all electron
Def2_TZVP31,32 basis set computational level. Geometry
optimizations were carried out without any constraints.
Optimized geometries were used as input for the ADF NMR
calculations. For the magnetic shielding tensor calculations (1H
and 13C), the zeroth-order regular approximation (ZORA)33−35
was used to include relativistic effects of both scalar and spin−
orbit contributions.36 The NMR calculations used an all-
electron triple-ζ basis set, which included two polarization
functions (i.e., TZ2P) and a PBE functional.
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(17) Chen, Y.; Callens, E.; Abou-Hamad, E.; Merle, N.; White, A. J.
ASSOCIATED CONTENT
* Supporting Information
The following file is available free of charge on the ACS
́
P.; Taoufik, M.; Coperet, C.; Le Roux, E.; Basset, J.-M. Angew. Chem.,
■
Int. Ed. 2012, 51, 11886−11889.
S
(18) Chen, Y.; Callens, E.; Abou-hamad, E.; Basset, J.-M. J.
Organomet. Chem. 2013, 744, 3−6.
(19) Chen, Y.; Ould-Chikh, S.; Callens, E.; Abou-Hamad, E.;
Mohandas, J. C.; Khalid, S.; Basset, J.-M. Organometallics 2014, 33,
1205−1211.
Information on optimized geometries and full disclosure
of the calculated magnetic shielding values for the
computational models used (PDF)
(20) (a) Bouhoute, Y.; Garron, A.; Grekov, D.; Merle, N.; Szeto, K.
C.; De Mallmann, A.; Del Rosal, I.; Maron, L.; Girard, G.; Gauvin, R.
M.; Delevoye, L.; Taoufik, M. ACS Catal. 2014, 4, 4232−4241. (b)
This work was presented at the ACS meeting in San Francisco, CA,
USA, Aug 12, 2014: Hamieh, A.; Chen, Y.; AbouHamad, E.; Goh, S.;
Emsley, L.; Basset, J.-M. In New Well Defined Silica-Supported Tungsten
Oxo Methyl Synthesized by Surface Alkylation: Application in Olefin and
Paraffin Metathesis; American Chemical Society: Washington, DC,
USA, Aug 10−14, 2014; CATL-175.
AUTHOR INFORMATION
Corresponding Author
■
Notes
The authors declare no competing financial interest.
†This work was presented at the 248th National Meeting of the
American Chemical Society in San Francisco, CA, USA, August
12, 2014.
́
(21) Blanc, F.; Basset, J.-M.; Coperet, C.; Sinha, A.; Tonzetich, Z. J.;
Schrock, R. R.; Solans-Monfort, X.; Clot, E.; Eisenstein, O.; Lesage, A.;
Emsley, L. J. Am. Chem. Soc. 2008, 130, 5886−5900.
(22) Weissermel, K.; Harpe, H. J. Industrial Organic Chemistry, 3rd
ed.; VCH: Weinheim, Germany, 1997.
ACKNOWLEDGMENTS
This work was supported by funds from King Abdullah
University of Science and Technology (KAUST).
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(23) Riache, N.; Callens, E.; Samantaray, M. K.; Kharbatia, N. M.;
Atiqullah, M.; Basset, J.-M. Chem.−Eur. J. 2014, 20, 15089−15094.
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