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

Baraa Werghi, Eva Pump, Mykyta Tretiakov, Edy Abou-Hamad, Andrei Gurinov, Pradeep Doggali, Dalaver H. Anjum, Luigi Cavallo, Anissa Bendjeriou-Sedjerari*, Jean Marie Basset

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

18 Scopus citations

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, [(Si-O-Si)(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.

Original languageEnglish (US)
Pages (from-to)3531-3537
Number of pages7
JournalChemical Science
Volume9
Issue number14
DOIs
StatePublished - 2018

Bibliographical note

Funding Information:
The research reported in this publication was supported by funding from King Abdullah University of Science and Technology (KAUST). The authors are grateful to the KAUST Supercomputing Laboratory (KSL) for the resources provided.

Publisher Copyright:
© 2018 The Royal Society of Chemistry.

ASJC Scopus subject areas

  • General Chemistry

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