Self-Metathesis of 1-Octene Using Alumina-Supported Re2O7 in Supercritical CO2

Fabris, Massimo; Aquino, Cindy; Ward, Antony J.; Perosa, Alvise; Maschmeyer, Thomas; Selva, Maurizio

doi:10.1007/s11244-008-9154-4

Cited by 6 publications

(6 citation statements)

References 32 publications

(45 reference statements)

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“…This product distribution matched our previous findings for the same reaction carried out under batch-CO 2 systems. 7,10 Although preliminary, these results proved that unprecedented reaction conditions obtained by the combination of a CF-scCO 2 reactor with Al 2 O 3 -supported Re 2 O 7 catalysts, were suitable for metathesis processes.…”

Section: The Apparatus For Continuous-flow Metathesis Reactionsmentioning

confidence: 76%

“…At 35°C and 90 bar, the maximum CF-conversion for the selfmetathesis of 1-octene (23%) is far lower than that (65-70%) obtained for the same reaction in the static mode. 7,10 Also, a CO 2 pressure dependence is observed for the CF-metathesis, while the corresponding batch process is insensitive to pressure effects. The reaction environment is therefore greatly differentiated when CF-dynamic or static conditions are used.…”

Section: Continuous-flow Vs Batch Conditions For Metathesis Reactions In Sccomentioning

confidence: 98%

“…Our previous investigations of batch metathesis reactions in scCO 2 demonstrated that Al 2 O 3 , preferably in the gamma phase, was by far the most convenient support among a number of different solids, including aluminosilicates and silica. 7,10 Since the objective of this work was to prove the feasibility of alkene metathesis under CF-scCO 2 conditions and to compare scCO 2 with conventional liquid solvents, only two catalytic systems based on Re 2 O 7 supported on γ-Al 2 O 3 were considered. They were prepared starting from NH 4 ReO 4 as the metal precursor, and commercial γ-Al 2 O 3 (Alfa-Aesar).…”

Section: The Catalystsmentioning

confidence: 99%

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Continuous-flow alkene metathesis: the model reaction of 1-octene catalyzed by Re2O7/γ-Al2O3 with supercritical CO2 as a carrier

et al. 2012

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In the presence of Re 2 O 7 supported on γ-Al 2 O 3 , the self-metathesis of 1-octene was conveniently carried out under continuous-flow (CF) conditions using supercritical CO 2 (scCO 2 ) as a carrier. This investigation allowed optimization of reaction parameters, the best values of which were found to be 100°C and 90 bar, operating at flow rates of 0.05 and 1 mL min −1 for 1-octene and scCO 2 , respectively, the reaction proceeded with very good self-metathesis selectivity (>90%) and an average productivity of ∼0.24 mL tetradecene g Re −1 min −1 . Although the catalyst was completely deactivated after the first 100-150 min of reaction, it could be recycled for (at least) five subsequent reactions without any loss of performance. The results provided incontrovertible evidence that for the investigated reaction, scCO 2 was a superior carrier with respect to conventional liquids, such as toluene or n-hexane.Scheme 1 † Electronic supplementary information (ESI) available: Details of TEM analysis and EDX spectra are reported for Re/Al WI2 catalyst. Also, representative GC-MS spectra of some components of the oil recovered after catalyst recycling, are shown. See

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Section: The Apparatus For Continuous-flow Metathesis Reactionsmentioning

confidence: 76%

Section: Continuous-flow Vs Batch Conditions For Metathesis Reactions In Sccomentioning

confidence: 98%

Section: The Catalystsmentioning

confidence: 99%

See 1 more Smart Citation

Continuous-flow alkene metathesis: the model reaction of 1-octene catalyzed by Re2O7/γ-Al2O3 with supercritical CO2 as a carrier

et al. 2012

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“…There are very few examples of rhenium-based metathesis catalysts obtained by a sol-gel method [24,25]. Non-hydrolytic sol-gel (NHSG) [26,27] is emerging as a powerful method to prepare tailored heterogeneous catalysts [28] and especially mesoporous mixed oxides [29].…”

Section: Introductionmentioning

confidence: 99%

Avoiding rhenium loss in non-hydrolytic synthesis of highly active Re–Si–Al olefin metathesis catalysts

Bouchmella

Stoyanova

Rodemerck

et al. 2015

Catalysis Communications

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“…Extensive efforts have been exerted to achieve olefin metathesis (OM) as it is a powerful tool for constructing carbon–carbon double bonds in organic synthesis and materials chemistry . Several Mo, Re, and Rh complexes have been used as OM catalysts, but critical shortcomings limit the use of these catalysts in many applications. After Grubbs synthesized and successfully applied a unique catalyst with Ru to norbornene synthesis, intense research efforts have yielded new insights into the details of OM, which is catalyzed using Ru complexes.…”

Section: Introductionmentioning

confidence: 99%

Reaction mechanism and Z‐selectivity for chelated Ru‐catalyzed AROCM of endic anhydride and propene: A DFT study

Zhu

Pang

Wang

2015

Int J of Quantum Chemistry

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Density functional theory calculations were performed to investigate the complete mechanism and selectivity for asymmetric ring opening cross‐metathesis of endic anhydride and propene through a chelated Ru catalyst with nitrato ligand. The preferred mechanism begins with the endic anhydride attacking the catalyst from the “side” position and forming a Ru four‐membered ring complex. Subsequently, the endic anhydride isomerizes with another four‐membered ring complex via the substituent groups rotating their locations. The ring then ruptures and leads to a Ru‐alkylidene complex. Afterward, propene reacts with the Ru‐alkylidene complex through a similar pathway, resulting in rapid a cycloaddition reaction, isomerization to undergo cycloreversion, and the release of (Z)‐ or (E)‐olefin homodimers. The overall preferred mechanism is in accordance with the mechanism of a previously reported chelated Ru catalyst containing a carboxylate ligand. The energy barrier of the transition state for cycloreversion differs by 2.72 kcal/mol from (Z)‐olefin to (E)‐olefin, indicating that the reaction has high Z‐selectivity, in accordance with experimental results. Moreover, cycloreversion is the rate‐determining step. The turnover frequency for selectivity is analyzed to determine the relationship between the theoretically computed catalytic cycle and its experimental counterpart. The activation strain was also analyzed to illustrate the mechanism from the point of quantum chemistry. All of the methods in this article were performed to explain the preference for Z‐olefin, which is attributed to a combination of the steric and electronic effects of the chelated catalyst. Finally, the catalyst is compared with the previously reported chelated Ru catalyst with a carboxylate ligand; results reveal that smaller nitrato sizes lead to higher selectivity efficiency of the catalyst. © 2015 Wiley Periodicals, Inc.

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Self-Metathesis of 1-Octene Using Alumina-Supported Re2O7 in Supercritical CO2

Cited by 6 publications

References 32 publications

Continuous-flow alkene metathesis: the model reaction of 1-octene catalyzed by Re2O7/γ-Al2O3 with supercritical CO2 as a carrier

Continuous-flow alkene metathesis: the model reaction of 1-octene catalyzed by Re2O7/γ-Al2O3 with supercritical CO2 as a carrier

Avoiding rhenium loss in non-hydrolytic synthesis of highly active Re–Si–Al olefin metathesis catalysts

Reaction mechanism and Z‐selectivity for chelated Ru‐catalyzed AROCM of endic anhydride and propene: A DFT study

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