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Issue 14, 2018
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Exploiting the interactions between the ruthenium Hoveyda–Grubbs catalyst and Al-modified mesoporous silica: the case of SBA15 vs. KCC-1

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Abstract

Immobilization of the 2nd generation Hoveyda–Grubbs catalyst HG-II onto well-ordered 2D hexagonal (SBA15) and 3D fibrous (KCC-1) mesostructured silica, which contained tetra-coordinated Al, has been investigated through the Surface Organometallic Chemistry (SOMC) methodology. The main interest of this study lies in the peculiarity of the silica supports, which display a well-defined tetrahedral aluminum hydride site displaying a strong Lewis acid character, [([triple bond, length half m-dash]Si–O–Si[triple bond, length half m-dash])([triple bond, length half m-dash]Si–O–)2Al–H]. The resulting supported Hoveyda–Grubbs catalysts have been fully characterized by advanced solid state characterization techniques (FT-IR, 1H and 13C solid state NMR, DNP-SENS, EF-TEM…). Together with DFT calculations, the immobilization of HG-II does not occur through the formation of a covalent bond between the complex and the Al-modified mesoporous silica as expected, but through an Al⋯Cl–[Ru]-coordination. It is not surprising that in functionalized olefin metathesis of diethyldiallyl malonate, DEDAM (liquid phase), leaching of the catalyst is observed which is not the case in non-functionalized olefin metathesis of propene (gas phase). Besides, the results obtained in propene metathesis with HG-II immobilized either on SBA15 (dpore = 6 nm) or KCC-1 (dpore = 4 or 8 nm) highlight the importance of the accessibility of the catalytic site. Therefore, we demonstrate that KCC-1 is a promising and suitable 3D mesoporous support to overcome the diffusion of reactants into the porous network of heterogeneous catalysts.

Graphical abstract: Exploiting the interactions between the ruthenium Hoveyda–Grubbs catalyst and Al-modified mesoporous silica: the case of SBA15 vs. KCC-1

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Publication details

The article was received on 07 Dec 2017, accepted on 05 Mar 2018 and first published on 05 Mar 2018


Article type: Edge Article
DOI: 10.1039/C7SC05200F
Citation: Chem. Sci., 2018,9, 3531-3537
  • Open access: Creative Commons BY license
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    Exploiting the interactions between the ruthenium Hoveyda–Grubbs catalyst and Al-modified mesoporous silica: the case of SBA15 vs. KCC-1

    B. Werghi, E. Pump, M. Tretiakov, E. Abou-Hamad, A. Gurinov, P. Doggali, D. H. Anjum, L. Cavallo, A. Bendjeriou-Sedjerari and J. Basset, Chem. Sci., 2018, 9, 3531
    DOI: 10.1039/C7SC05200F

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