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Ru complexes of Hoveyda-Grubbs type immobilized on lamellar zeolites: activity in olefin metathesis reactions.

Ru complexes of Hoveyda-Grubbs type immobilized on lamellar zeolites: activity in olefin metathesis reactions.

Beilstein journal of organic chemistry (2015-12-15)

Hynek Balcar, Naděžda Žilková, Martin Kubů, Michal Mazur, Zdeněk Bastl, Jiří Čejka

ABSTRACT

Hoveyda-Grubbs type catalysts with cationic tags on NHC ligands were linker-free immobilized on the surface of lamellar zeolitic supports (MCM-22, MCM-56, MCM-36) and on mesoporous molecular sieves SBA-15. The activity of prepared hybrid catalysts was tested in olefin metathesis reactions: the activity in ring-closing metathesis of citronellene and N,N-diallyltrifluoroacetamide decreased in the order of support MCM-22 ≈ MCM-56 > SBA-15 > MCM-36; the hybrid catalyst based on SBA-15 was found the most active in self-metathesis of methyl oleate. All catalysts were reusable and exhibited low Ru leaching (<1% of Ru content). XPS analysis revealed that during immobilization ion exchange between Hoveyda-Grubbs type catalyst and zeolitic support occurred in the case of Cl(-) counter anion; in contrast, PF6 (-) counter anion underwent partial decomposition.

MATERIALS

Product Number

Brand

Product Description

Sigma-Aldrich

Methyl stearate, ≥96%, FG

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Methyl stearate, ~99% (GC)

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Methyl palmitate, ≥99% (capillary GC)

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Toluene, SAJ first grade, ≥99.0%

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Toluene, JIS 300, for residue analysis, ≥99.8%

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Toluene, JIS 1000, for residue analysis, ≥99.8%

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Dichloromethane, JIS special grade, ≥99.0%

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Toluene, suitable for HPLC, ≥99.9%

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Aluminum oxide, nanowires, diam. × L 2-6 nm × 200-400 nm

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Dichloromethane, suitable for HPLC, ≥99.9%, contains 40-150 ppm amylene as stabilizer

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cis-3-Hexenyl acetate, ≥98%, stabilized, FCC, FG

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Dichloromethane, anhydrous, ≥99.8%, contains 40-150 ppm amylene as stabilizer

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Aluminum oxide, 99.997% trace metals basis

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Aluminum oxide, nanopowder, 13 nm primary particle size (TEM), 99.8% trace metals basis

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Toluene, ACS reagent, ≥99.5%

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Aluminum oxide, activated, basic, Brockmann I

Sigma-Aldrich

Toluene, ACS reagent, ≥99.5%

Sigma-Aldrich

Dichloromethane, ACS reagent, ≥99.5%, contains 40-150 ppm amylene as stabilizer