Direct observation of reaction intermediates for a well defined heterogeneous alkene metathesis catalyst.

Proceedings of the National Academy of Sciences of the United States of America
Frédéric BlancRichard R Schrock

Abstract

Grafting of [W([triple bond]NAr)(=CHtBu)(2,5-Me(2)NC(4)H(2))(2)] on a silica partially dehydroxylated at 700 degrees C (SiO(2- (700))) generates the corresponding monosiloxy complex [([triple bond]SiO)W([triple bond]NAr)(=CHtBu)(2,5-Me(2)NC(4)H(2))] as the major species (approximately 90%) along with [([triple bond]SiO)W([triple bond]NAr)(CH(2)tBu)(2,5-Me(2)NC(4)H(2))(2)], according to mass balance analysis, IR, and NMR studies. This heterogeneous catalyst displays good activity and stability in the metathesis of propene. Very importantly, solid state NMR spectroscopy allows observation of the propagating alkylidene as well as stable metallacyclobutane intermediates. These species have the same reactivity as the initial surface complex [([triple bond]SiO)W([triple bond]NAr)(=CHtBu)(2,5-Me(2)NC(4)H(2))], which shows that they are the key intermediates of alkene metathesis.

References

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Dec 15, 2006·Journal of the American Chemical Society·Anna G Wenzel, Robert H Grubbs
Jan 25, 2007·Journal of the American Chemical Society·Patricio E Romero, Warren E Piers
Feb 1, 2007·Journal of the American Chemical Society·Frédéric BlancRichard R Schrock
Jun 15, 2007·Journal of the American Chemical Society·Albert PoaterOdile Eisenstein
Jun 19, 2007·Journal of the American Chemical Society·Frédéric BlancRichard R Schrock
Nov 29, 2007·Dalton Transactions : an International Journal of Inorganic Chemistry·Christophe Copéret

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Citations

Apr 2, 2011·Journal of the American Chemical Society·Anna G WenzelRobert H Grubbs
Dec 7, 2013·Journal of the American Chemical Society·Matthew P ConleyRichard R Schrock
Jun 6, 2009·Journal of the American Chemical Society·Annie J JiangRichard R Schrock
Feb 3, 2011·Beilstein Journal of Organic Chemistry·Christophe Copéret
May 4, 2016·Journal of the American Chemical Society·Maxence VallaPhilippe Sautet
Sep 10, 2016·ACS Central Science·Victor MougelChristophe Copéret
Dec 21, 2016·Journal of the American Chemical Society·Pierrick BerruyerLyndon Emsley
Jul 8, 2017·Angewandte Chemie·Christophe CopéretPavel A Zhizhko
Oct 30, 2016·Angewandte Chemie·Deven P EstesChristophe Copéret
Feb 5, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Xavier Solans-Monfort
Mar 13, 2014·Chemical Communications : Chem Comm·E CallensJ M Basset
Apr 22, 2010·Analytical Chemistry·Shi BaiCecil Dybowski
Aug 5, 2017·ACS Central Science·Christopher P GordonOdile Eisenstein
Jun 29, 2017·Journal of the American Chemical Society·Christophe CopéretTa-Chung Ong
Apr 3, 2019·ACS Central Science·Brennan J WalderLyndon Emsley

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