Synthesis Optimization and Catalytic Activity Screening of Industrially Relevant Ruthenium-Based Metathesis Catalysts

Olefin metathesis is a powerful catalytic reaction that has a huge potential in the pharmaceutical, polymer and specialty chemicals industries. Cost-effective industrial applications require large-scale availability of catalyst precursors which combine high activity, high selectivity and long life-time. Among the known numerous families of olefin metathesis catalysts, the Umicore M7-catalyst family represents a novel class of Hoveyda-type complexes showing excellent chemical stabilities and modular activity profiles. Relevant aspects related to their industrial synthesis as well as their catalytic performance in valuable olefin metathesis transformations are overviewed here.     

Fatty acid methyl ester heterogeneous self‐metathesis in hydrophobic green solvent: Mass transfer limitations,catalyst recyclability,and stability

The role of room‐temperature ionic liquids (RTILs), [bmim][PF₆] and [bmim][Tf₂N], as reaction media regarding the catalytic activity and stability of methyltrioxorhenium (MTO) supported on ZnCl₂‐modified mesoporous Al₂O₃ has been studied for self‐metathesis of a functionalized olefin, methyl oleate. The humidity influence on the catalytic activity was probed. The catalyst recycling ability and the kinetics of the metathesis reaction using these RTILs were also investigated. It was found that the MTO‐based catalyst was efficient in viscous hydrophobic RTIL solvents. However, their high viscosity was found to increase the mass transfer limitations thus somewhat impacting the reaction kinetics. Nevertheless, better catalyst stability was reached allowing its possible recycling when used in RTIL media.     

Investigation of the preparation and catalytic activity of supported Mo,W, and Re oxides as heterogeneous catalysts in olefin metathesis

For several decades olefin metathesis reactions over supported Mo, W, and Re oxides catalysts have attracted remarkable interest owning to their growing industrial applications. Therefore, particular attention was devoted to improve the catalytic activity of these catalysts. In the way of exploration of the catalytic performances of these heterogeneous Mo, W, and Re oxides systems, it was found that high dispersion of metal oxide on the support surface and the oxidation state of the metal oxide on the surface of catalyst play crucial factors on the catalysts efficiency. Importantly, these factors have an origin in the preparation methods and the properties of the used supports. In this regard, we have tried to address the various preparation methods of immobilized Mo, W, and Re oxide catalysts as well as properties of supporting material to better understand their impacts on the catalytic performances of these catalysts.     

Ruthenium‐Indenylidene Complexes: Scope in Cross‐Metathesis Transformations

A comparative study examining the catalytic activity of a series of five indenylidene‐containing ruthenium complexes in olefin cross‐metathesis reactions is presented. Results reveal the greater efficiency of precatalyst 5 , highlighting the key role of the N,N′‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene (IPr) ligand for this transformation. The scope of this precatalyst was investigated and several microwave experiments were carried out allowing for catalyst loadings as low as 0.1 mol%. Overall, cross‐metathesis products were isolated in moderate to excellent yields with high stereoselectivity.     

A Highly Active and Reusable Heterogeneous Ruthenium Catalyst for Olefin Metathesis

The synthesis and characterization of Ru complexes of the type [L₂X₂RuCHR] (L=PPh₃, PCy₃, N‐heterocyclic carbenes or their derivates; X=Cl) grafted on mesoporous SBA‐15 material are described. In this heterogeneous catalyst the Ru complexes are anchored in the pore channels of mesoporous silica material SBA‐15 to prevent the decomposition of the catalytic species. Compared with formal organic‐supported heterogeneous catalysts, this heterogeneous catalyst shows relatively high catalytic activity in olefin metathesis reactions and can be used several times without any decrease in catalytic activities.     

Synthesis of polyethylene/polyester copolymers through main chain exchange reactions via olefin metathesis

The synthesis and characterization of linear polyethylene/polyester copolymers produced by olefin cross metathesis and subsequent catalytic hydrogenation are described. The success of the scrambling reaction between 1,4-polybutadiene and unsaturated polyester via olefin cross metathesis was confirmed by ¹H NMR. Differential scanning calorimetric (DSC) measurements indicated that the size of the copolymer blocks varied gradually with the exchange ratio. Catalytic hydrogenation of the unsaturated copolymers with different exchange ratios was carried out using Pd–Al₂O₃. The crystallinity of the resulting hydrogenated polymers depended on the exchange ratios achieved during olefin cross metathesis. This suggests that the unique sequential structure imparted to the unsaturated polymers during metathesis was retained during the hydrogenation process.     

Olefin epoxidation with metal-based nanocatalysts

Alkene epoxidations are an important class of reactions carried out in industry; however, current methods are plagued by problems, including high cost, difficulty in recovering catalysts, and generation of large quantities of acidic and chlorinated waste. In recent years, nanocatalysts have been considered as robust, heterogeneous alternatives to homogeneous catalysts. This work evaluates silver- and base metal-containing nanocatalysts as olefin epoxidation catalysts, highlighting the industrial applicability and green aspects of these catalytic systems. The nanocatalysts discussed are mostly supported or composite materials that showed (generally) good activity and selectivity for various/multiple olefin epoxidation reactions.     

Selective oxidation of ethane and propane over sulfated zirconia‐supported nickel oxide catalysts

The oxidative dehydrogenations of ethane and propane were investigated over a series of zirconia and nickel‐oxide supported on zirconia catalysts. It was found that zirconia, sulfated zirconia as well as NiO‐based zirconia catalysts showed high catalytic activities for oxidative dehydrogenation of ethane and propane. However, conversion and selectivity differed depending on the nature of the catalysts. Zirconia, sulfated zirconia (SZ) and their supported NiO catalysts showed high ethane conversions but lesser selectivities to olefins while NiO/Li₂ZrO₃ exhibited high selectivities to ethylene and propylene. Addition of an LiCl promoter in the NiO/SZ catalyst increased the catalytic activity and olefin selectivity, thus resulting in a higher olefin yield. In the oxidative dehydrogenations of ethane and propane NiO–LiCl/SZ exhibited 79% ethylene selectivity at 93% ethane conversion at 650 °C and 52% selectivity to propylene at 20% propane conversion at 600 °C, respectively. Characterization showed that the physico‐chemical properties of the catalysts determine the catalytic activity and selectivity. © 2001 Society of Chemical Industry     

A tracer study of the metathesis of simple olefins over molybdena-alumina catalysts

Metathesis of perdeuterio- and perhydroethene, propene, 1-butene, and their mixtures with cis-2-butene was studied over a molybdena-alumina catalyst using recirculation and pulse systems. No metathesis was observed over a fresh unreduced catalyst, but after pretreatment with cis-2-butene the reactivity of olefins in metathesis reactions increased in the sequence of ethene ? 1-butene < propene < cis-2-butene. The activity was higher for the metathesis of propene or 1-butene after the catalyst was pretreated with the corresponding olefin instead of cis-2-butene, but no metathesis was induced by ethene. Metathesis of cis-2-butene was suppressed by the addition of equal amounts of olefins in the sequence: ethene ? 1-butene < propene. Studies of mixtures revealed that the rate of cis- to trans-2-butene isomerization by metathesis ～- the rate of degenerate metathesis of 1-butene or the cross metathesis of 1-butene with 2-butene.     

Zur Oligomerisierung von Cycloolefinen in Gegenwart zirkonhaltiger Katalysatorsysteme

On the Oligomerization of Cyclic Alkenes in the Presence of Zirconium-containing Catalytic Systems In connection with investigations on olefin metathesis we studied the reaction of cyclic olefins C₅ C₈ and C₁₂ in the presence of zirconium-containing catalytic systems in the homogeneous liquid phase. The influence of different zirconium compounds on the reaction run off and on the distribution of the reaction products was examined in the presence and the absence of Lewis acids. The reaction products could be separated and identified by a combination of distillation, chromatographical, chemical and spectrometrical methods. The results show that under the conditions mentioned a metathetic polymerization and a normal olefin oligomerization take place simultaneously.     

Propylene conversion reactions; metathesis,cyclization and hydrogenolysis catalyzed by Mo(100) and oxygen-covered Mo(100)

Analysis of the products formed in the Mo(100) single crystal-catalyzed decomposition of propylene using an isolatable high-pressure reactor shows that this surface simultaneously catalyzes metathesis, hydrogenolysis and also methylcyclopropane formation. The activation energy for olefin metathesis on Mo(100) is measured to be 65±1 kcal/mole, and the reaction is first order in propylene pressure. These results are consistent with the reaction proceeding via a carbene mechanism on Mo(100) since hydrogenolysis indicates that carbon-carbon bonds can cleave selectively, and methylcyclopropane formation suggests that a metallacycle has formed. The observed first-order reaction kinetics are also in accord with this view. Pre-dosing the Mo(100) surface with a monolayer of oxygen reduces the catalytic activity by a factor of 17. This implies that the four-fold hollow site is active for propylene metathesis on Mo(100) since atomic oxygen adsorbs at this site.     

低碳烯烃聚合催化剂的研究新进展

介绍了近年来烯烃聚合催化剂研究所取得的一些新进展,它们包括Ziegler-Natta催化剂、茂金属催化剂、非茂金属催剂、某些亚胺类后过渡金属(Ni、Pd、Fe、Co)配合物催化剂以及其它用于烯烃聚合的新型催化剂等。对世界一些主要石化公司生产PE及PP所采用的催化剂近况也作了简单表述。目前世界茂金属催化剂发展迅速,对于烯烃聚合新品种的开发具有潜在而广阔的工业应用前景和重要价值。     

Salicylaldimine Ruthenium Alkylidene Complexes: Metathesis Catalysts Tuned for Protic Solvents

Tuning the electronic and steric environment of olefin metathesis catalysts with specialized ligands can adapt them to broader applications, including metathesis in aqueous solvents. Bidentate salicylaldimine ligands are known to stabilize ruthenium alkylidene complexes, as well as allow ring‐closing metathesis in protic media. Here, we report the synthesis and characterization of exceptionally robust olefin metathesis catalysts bearing both bidentate salicylaldimine and N‐heterocyclic carbene ligands, including a trimethylammonium‐functionalized complex adapted for polar solvents. NMR spectroscopy and X‐ray crystallographic analysis confirm the structures of the complexes. Although the N‐heterocyclic carbene–salicylaldimine ligand combination limits the activity of these catalysts in non‐polar solvents, this pairing enables efficient ring‐closing metathesis of both dienes and enynes in methanol and methanol/water mixtures under air.     

低碳烯烃聚合催化剂的研究新进展

介绍了近来来烯烃聚合催化剂研究所取得的一些新进展,它们包括Ziegler-Natta催化剂、茂金属催化剂、非茂金属催剂、某些亚胺类后过渡金属(Ni、Pd、Fe、Co)配合物催化剂以及其它用于烯烃聚合的新型催化剂等。对世界一些主要石化公司生产PE及PP所采用的催化剂近况也作了简单表述。目前世界茂金属催化剂发展迅速,对于烯烃聚合新品种的开发具有潜在而广阔的工业应用前景和重要价值。     

Well‐Defined End‐Functionalized Conjugated Polymers/Oligomers Exhibiting Unique Emission Properties through the End Groups: The Exclusive Synthesis by Combined Olefin Metathesis with Wittig‐type Coupling

Acyclic diene metathesis polymerization using ruthenium–carbene catalysts affords defect‐free, high molecular weight poly(arylene vinylene)s containing all trans olefinic double bonds. The exclusive end‐functionalization in the resultant poly(fluorene vinylene)s or poly(phenylene vinylene)s can be attained by treating the vinyl end groups using a molybdenum–alkylidene catalyst/reagent (through olefin metathesis) followed by addition of various aldehydes (Wittig‐type coupling). Some of these end‐modified conjugated materials display unique emission properties, which are different from the original ones, through an interaction (energy transfer or structural change in the excited state) between the conjugated main chain and the end groups [oligo(thiophene)s, F‐BODIPY, etc.]. Exclusive synthesis of well‐defined, all‐trans end‐functionalized oligo(2,5‐dialkoxy‐1,4‐phenylene vinylene)s [(oligo(phenylene vinylene), alkoxy = O(CH₂)₂OSiⁱ Pr₃, up to 31 repeat units] is demonstrated by adopting a stepwise synthetic approach (olefin metathesis and the subsequent Wittig‐type cleavage). It is clearly demonstrated that their optical properties (especially the fluorescence spectra including photoluminescence quantum yields) are strongly affected by the end groups as well as the conjugation repeat units.     

Hoveyda-Grubbs type metathesis catalyst immobilized on mesoporous molecular sieves—The influence of pore size on the catalyst activity

New hybrid olefin metathesis catalysts were prepared by immobilization of Hoveyda-Grubbs type catalyst (commercially available as Zhan catalyst-1B) on the surface of mesoporous molecular sieves differing in pore size and architecture (MCM-41, MCM-48, and SBA-15) and conventional silica for a comparison. The activity of these catalysts was tested in RCM of (−)-β-citronellene, metathesis of 1-decene, ADMET of 1,9-decadiene, and in ROMP of cyclooctene and was found to increase significantly with the increasing pore size of the supports used. In all reactions, the activity of hybrid catalysts based on mesoporous molecular sieves was higher than that of catalyst using conventional silica as a support. In ROMP of cyclooctene, high molecular weight polymer (M_w = 300,000) in high yield (70-80%) was obtained with catalysts based on mesoporous supports, however, only 40% polymer yield was obtained using catalyst based on conventional silica.     

第三代降烯烃催化剂GOR-Ⅲ的开发和工业应用

针对进一步增强催化剂的降烯烃能力、汽油辛烷值不降或少降、提高重油裂化能力和改善产品的市场需求,开发了第三代降烯烃催化剂GORⅢ并进行了工业应用。工业应用结果表明,采用新型基质材料ASP、改性活性组分制备的GORⅢ催化剂降烯烃能力强,同时能在一定程度上提高稳定汽油的辛烷值,且汽油的诱导期延长,催化汽油性质有所改善。GORⅢ催化剂具有活性高、重油裂化能力强,产品选择性好,轻质油收率高等优点。     

Comparative Investigation of Hoveyda–Grubbs Catalysts bearing Modified N‐Heterocyclic Carbene Ligands

This paper reports the structural modification of Hoveyda–Grubbs complexes through the introduction of either an N‐alkyl‐N′‐mesityl heterocyclic carbene, an N‐alkyl‐N′‐(2,6‐diisopropylphenyl) heterocyclic carbene, or an N‐alkyl‐N′‐alkyl heterocyclic carbene. The effect of the modified N‐heterocyclic carbene (NHC) ligand was investigated in representative ring‐opening metathesis polymerization (ROMP), ring‐closing metathesis (RCM) and cross metathesis (CM) reactions. A pronounced influence on both catalyst activity and selectivity was found to be exerted by the NHC amino substituents, which emphasizes that a rigorously selected steric environment is critical in olefin metathesis catalyst design.     

SBA-15 Immobilized Ruthenium Carbenes as Catalysts for Ring Closing Metathesis and Ring Opening Metathesis Polymerization

New hybrid catalysts for olefin metathesis were prepared by immobilization of Hoveyda–Grubbs type Ru alkylidenes on a siliceous SBA-15 support via exchange of chloro ligands for substituted carboxylates. Catalysts proved a high activity in ring closing metathesis of 1,7-octadiene and diethyl diallylmalonate, reusability and low Ru leaching. In Ring Opening Metathesis Polymerization of norbornene and cyclooctene, SBA-15 supported catalyst gave higher yields of high-molecular-weight polymers than corresponding catalyst with conventional silica support.     

Efficient Heterogeneous Dual Catalyst Systems for Alkane Metathesis

A fully heterogeneous and highly efficient dual catalyst system for alkane metathesis (AM) has been developed. The system is comprised of an alumina‐supported iridium pincer catalyst for alkane dehydrogenation/olefin hydrogenation and a second heterogeneous olefin metathesis catalyst. The iridium catalysts bear basic functional groups on the aromatic backbone of the pincer ligand and are strongly adsorbed on Lewis acid sites on alumina. The heterogeneous systems exhibit higher lifetimes and productivities relative to the corresponding homogeneous systems as catalyst/catalyst interactions and bimolecular decomposition reactions are inhibited. Additionally, using a “two‐pot” device, the supported Ir catalysts and metathesis catalysts can be physically separated and run at different temperatures. This system with isolated catalysts shows very high turnover numbers and is selective for the formation of high molecular weight alkanes.