Heterolytic Activation of C-H Bonds on Cr(III)-O Surface Sites Is a Key Step in Catalytic Polymerization of Ethylene and Dehydrogenation of Propane

Inorganic Chemistry
Matthew P ConleyChristophe Copéret

Abstract

We describe the reactivity of well-defined chromium silicates toward ethylene and propane. The initial motivation for this study was to obtain a molecular understanding of the Phillips polymerization catalyst. The Phillips catalyst contains reduced chromium sites on silica and catalyzes the polymerization of ethylene without activators or a preformed Cr-C bond. Cr(II) sites are commonly proposed active sites in this catalyst. We synthesized and characterized well-defined chromium(II) silicates and found that these materials, slightly contaminated with a minor amount of Cr(III) sites, have poor polymerization activity and few active sites. In contrast, chromium(III) silicates have 1 order of magnitude higher activity. The chromium(III) silicates initiate polymerization by the activation of a C-H bond of ethylene. Density functional theory analysis of this process showed that the C-H bond activation step is heterolytic and corresponds to a σ-bond metathesis type process. The same well-defined chromium(III) silicate catalyzes the dehydrogenation of propane at elevated temperatures with activities similar to those of a related industrial chromium-based catalyst. This reaction also involves a key heterolytic C-H bond activation step...Continue Reading

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Citations

Jul 26, 2015·Proceedings of the National Academy of Sciences of the United States of America·Murielle F DelleyChristophe Copéret
Jul 2, 2016·Chemical Reviews·Matthew E O'ReillyAdam S Veige
Jul 12, 2016·Chemical Reviews·Christophe CopéretKeith Searles
Oct 22, 2016·Journal of the American Chemical Society·Deven P EstesChristophe Copéret
Jul 4, 2017·Inorganic Chemistry·Deven P EstesChristophe Copéret
Jun 6, 2017·Journal of the American Chemical Society·Murielle F DelleyChristophe Copéret
Jul 8, 2017·Angewandte Chemie·Christophe CopéretPavel A Zhizhko
Sep 5, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Ryuki BabaToshiaki Taniike
Sep 29, 2018·Angewandte Chemie·Damien B Culver, Matthew P Conley
Mar 23, 2017·Chemical Communications : Chem Comm·Aleix Comas-VivesChristophe Copéret
Jan 26, 2021·Chemical Society Reviews·Sai ChenJinlong Gong
Apr 21, 2021·Nature Communications·Nicole J LiBrettoJeffrey T Miller
May 12, 2021·Journal of the American Chemical Society·David TrummerChristophe Copéret
May 12, 2021·Chemical Society Reviews·Scott R DochertyChristophe Copéret
Oct 16, 2019·Chemical Reviews·Manoja K SamantarayJean-Marie Basset
Aug 28, 2018·Journal of the American Chemical Society·Keith SearlesChristophe Copéret
Jun 2, 2015·Inorganic Chemistry·Etsuko Fujita, Alan S Goldman
Mar 23, 2019·Journal of the American Chemical Society·Zoha H SyedMassimiliano Delferro
Oct 22, 2020·Chemical Reviews·Selina K KaiserJavier Pérez-Ramírez
Aug 23, 2017·Journal of the American Chemical Society·Caterina BarzanElena Groppo

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