Rhenium-tungsten mixture

Olefin metathesis is the transition-metal-catalyzed inter- or intramolecular exchange of alkylidene units of alkenes. The metathesis of propene is the most simple example in the presence of a suitable catalyst, an equilibrium mixture of ethene, 2-butene, and unreacted propene is obtained (Eq. 1). This example illustrates one of the most important features of olefin metathesis its reversibility. The metathesis of propene was the first technical process exploiting the olefin metathesis reaction. It is known as the Phillips triolefin process and was run from 1966 till 1972 for the production of 2-butene (feedstock propene) and from 1985 for the production of propene (feedstock ethene and 2-butene, which is nowadays obtained by dimerization of ethene). Typical catalysts are oxides of tungsten, molybdenum or rhenium supported on silica or alumina [ 1 ]. 

A platinum-rhenium composite catalyst supported on the granular activated carbon (Pt-Re/C, 5 wt-Pt%, mixed molar ratio of Pt/Re = 2) [10] was prepared by a "dry-migration method" [33,34] as follows (1) The Pt/C catalyst prepared earlier (5 wt-metal%) was evacuated at 180°C for 1 h (2) The mixture (molar ratio of Pt/Re = 2) of the Pt/C catalyst and a cyclopentadienylrhenium tricarbonyl complex (Re(Cp)(CO)3) were stirred under nitrogen atmosphere at room temperature for 1 h and then heated at 100° for 1 h, with the temperature kept at a constant (3) This mixture was further stirred under hydrogen atmosphere at 240°C for 3 h and finally (4) the Pt-Re/C composite catalyst was evacuated at 180°C for 1 h. A platinum-tungsten composite catalyst supported on the granular activated carbon (Pt-W/C, 5 wt-Pt%, mixed molar ratio of Pt/W = 1) [5,6] was also prepared similarly by the dry-migration method. All the catalysts were evacuated inside the reactor at 150°C for 1 h before use. 

It was later found that some aldehyde complexes of rhenium, [Re(NO) (PPh3) 0=C(Aryl)H (Tj-C5H5)]BF4, are also present in solution as a rapidly interconverting mixture of rf isomers and the if isomer.48,49 With the exception of solvent dependence, similar dependencies of the equilibrium constants on the aryl substituents and on the temperature were observed. The solvent dependence was found to be opposite, which, however, is easily understood when taking into account that the rhenium aldehyde complexes are cationic whereas the chromium and tungsten thio- and selenoaldehyde complexes are neutral. 

Vanhoye and coworkers [402] synthesized aldehydes by using the electrogenerated radical anion of iron pentacarbonyl to reduce iodoethane and benzyl bromide in the presence of carbon monoxide. Esters can be prepared catalytically from alkyl halides and alcohols in the presence of iron pentacarbonyl [403]. Yoshida and coworkers reduced mixtures of organic halides and iron pentacarbonyl and then introduced an electrophile to obtain carbonyl compounds [404] and converted alkyl halides into aldehydes by using iron pentacarbonyl as a catalyst [405,406]. Finally, a review by Torii [407] provides references to additional papers that deal with catalytic processes involving complexes of nickel, cobalt, iron, palladium, rhodium, platinum, chromium, molybdenum, tungsten, manganese, rhenium, tin, lead, zinc, mercury, and titanium. 

The initial observation of a metal carbene that reacted with an alkene to give a metallacyclobutane complex was reported by Osborn and coworkers for the reaction shown in equation (10). This reaction was observed by NMR spectroscopy at low temperature (—70°C). When this reaction mixture was allowed to warm to higher temperature, polynorbornene was produced in high yield. Shortly after this discovery, the titanocene complex (4) was shown to be an efficient catalyst for the synthesis of monodisperse polynorbornenes. These discoveries, along with the synthesis of a new family of tungsten (5a), molybdenum (5b), and rhenium (6) catalysts,shown in Figure 1, have opened a new era of ROMP chemistry in which the polymer synthesis is guided by the selection of a catalyst... 

The following metal compounds are used for the preparation of the catalysts oxides, metal carbonyls, halides, alkyl and allyl complexes, as well as molybdenum, tungsten, and rhenium sulfides. Oxides of iridium, osmium, ruthenium, rhodium, niobium, tantalum, lanthanum, tellurium, and tin are effective promoters, although their catalytic activity is considerably lower. Oxides of aluminum, silicon, titanium, manganese, zirconium as well as silicates and phosphates of these elements are utilized as supports. Also, mixtures of oxides are used. The best supports are those of alumina oxide and silica. 

Metathesis disproportionation of propene has been reported on a wide range of heterogeneous catalytic systems based mainly on earbonyl eom-poxmds, as well as oxides or sulfides of molbyde-num, tungsten, or rhenium supported on alumina, silica, or mixtures of oxides or phosphates. Among these catalytic systems, only a restricted number present good activity and sufficient selectivity to allow reasonable yields of ethene and 2-butene. Examples of the most efficient heterogeneous catalysts appear in Table 2 [1, 3, 5-11]. 

All methyl isomers of norbornene, 1-, 2-, 5-, and 7-methylnorbornene have been reacted in the presence of catalysts based on tungsten, rhenium, ruthenium, osmium and iridium compounds [7]. The polymers corresponded to ring-opened products having various microstructures. Racemic mixtures or pure enantiomers have been used as starting materials. Differences in reactivities as a function of the methyl position (1, 2, 5 or 7) and steric configuration (endo-exo and syn-anti) have been reported. 

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