Details
| Original language | English |
|---|---|
| Pages (from-to) | 16369-16382 |
| Number of pages | 14 |
| Journal | Chemistry - A European Journal |
| Volume | 18 |
| Issue number | 51 |
| Publication status | Published - 22 Oct 2012 |
Abstract
In this study, a new pyridinium-tagged Ru complex was designed and anchored onto sulfonated silica, thereby forming a robust and highly active supported olefin-metathesis pre-catalyst for applications under batch and continuous-flow conditions. The involvement of an oxazine-benzylidene ligand allowed the reactivity of the formed Ru pre-catalyst to be efficiently controlled through both steric and electronic activation. The oxazine scaffold facilitated the introduction of the pyridinium tag, thereby affording the corresponding cationic pre-catalyst in good yield. Excellent activities in ring-closing (RCM), cross (CM), and enyne metathesis were observed with only 0.5mol % loading of the pre-catalyst. When this powerful pre-catalyst was immobilized onto a silica-based cationic-exchange resin, a versatile catalytically active material for batch reactions was generated that also served as fixed-bed material for flow reactors. This system could be reused at 1mol % loading to afford metathesis products in high purity with very low ruthenium contamination under batch conditions (below 5ppm). Scavenging procedures for both batch and flow processes were conducted, which led to a lowering of the ruthenium content to as little as one tenth of the original values. Tag! You're it! A pyridinium-tagged Ru complex (see figure) that was anchored to sulfonated silica formed a robust and highly active supported olefin-metathesis pre-catalyst for applications under batch and continuous-flow conditions with low ruthenium leaching.
Keywords
- flow reactors, immobilization, olefin metathesis, ruthenium, supported catalysts
ASJC Scopus subject areas
- Chemical Engineering(all)
- Catalysis
- Chemistry(all)
- Organic Chemistry
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In: Chemistry - A European Journal, Vol. 18, No. 51, 22.10.2012, p. 16369-16382.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - A fast-initiating ionically tagged ruthenium complex
T2 - A robust supported pre-catalyst for batch-process and continuous-flow olefin metathesis
AU - Borré, Etienne
AU - Rouen, Mathieu
AU - Laurent, Isabelle
AU - Magrez, Magaly
AU - Caijo, Fréderic
AU - Crévisy, Christophe
AU - Solodenko, Wladimir
AU - Toupet, Loic
AU - Frankfurter, René
AU - Vogt, Carla
AU - Kirschning, Andreas
AU - Mauduit, Marc
PY - 2012/10/22
Y1 - 2012/10/22
N2 - In this study, a new pyridinium-tagged Ru complex was designed and anchored onto sulfonated silica, thereby forming a robust and highly active supported olefin-metathesis pre-catalyst for applications under batch and continuous-flow conditions. The involvement of an oxazine-benzylidene ligand allowed the reactivity of the formed Ru pre-catalyst to be efficiently controlled through both steric and electronic activation. The oxazine scaffold facilitated the introduction of the pyridinium tag, thereby affording the corresponding cationic pre-catalyst in good yield. Excellent activities in ring-closing (RCM), cross (CM), and enyne metathesis were observed with only 0.5mol % loading of the pre-catalyst. When this powerful pre-catalyst was immobilized onto a silica-based cationic-exchange resin, a versatile catalytically active material for batch reactions was generated that also served as fixed-bed material for flow reactors. This system could be reused at 1mol % loading to afford metathesis products in high purity with very low ruthenium contamination under batch conditions (below 5ppm). Scavenging procedures for both batch and flow processes were conducted, which led to a lowering of the ruthenium content to as little as one tenth of the original values. Tag! You're it! A pyridinium-tagged Ru complex (see figure) that was anchored to sulfonated silica formed a robust and highly active supported olefin-metathesis pre-catalyst for applications under batch and continuous-flow conditions with low ruthenium leaching.
AB - In this study, a new pyridinium-tagged Ru complex was designed and anchored onto sulfonated silica, thereby forming a robust and highly active supported olefin-metathesis pre-catalyst for applications under batch and continuous-flow conditions. The involvement of an oxazine-benzylidene ligand allowed the reactivity of the formed Ru pre-catalyst to be efficiently controlled through both steric and electronic activation. The oxazine scaffold facilitated the introduction of the pyridinium tag, thereby affording the corresponding cationic pre-catalyst in good yield. Excellent activities in ring-closing (RCM), cross (CM), and enyne metathesis were observed with only 0.5mol % loading of the pre-catalyst. When this powerful pre-catalyst was immobilized onto a silica-based cationic-exchange resin, a versatile catalytically active material for batch reactions was generated that also served as fixed-bed material for flow reactors. This system could be reused at 1mol % loading to afford metathesis products in high purity with very low ruthenium contamination under batch conditions (below 5ppm). Scavenging procedures for both batch and flow processes were conducted, which led to a lowering of the ruthenium content to as little as one tenth of the original values. Tag! You're it! A pyridinium-tagged Ru complex (see figure) that was anchored to sulfonated silica formed a robust and highly active supported olefin-metathesis pre-catalyst for applications under batch and continuous-flow conditions with low ruthenium leaching.
KW - flow reactors
KW - immobilization
KW - olefin metathesis
KW - ruthenium
KW - supported catalysts
UR - http://www.scopus.com/inward/record.url?scp=84870925551&partnerID=8YFLogxK
U2 - 10.1002/chem.201201589
DO - 10.1002/chem.201201589
M3 - Article
AN - SCOPUS:84870925551
VL - 18
SP - 16369
EP - 16382
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
IS - 51
ER -