Rhenium , reaction

No data exist for rhenium reactions to support one chemical sequence over the other. The best that one can do is present arguments on the basis of precedent and plausibility. Nonetheless, an argument against the first assignment can be made, and another in favor of the second. 

As the five-electron donor converts to a one-electron donor. Re accepts an additional four electrons from the two trimethylphosphine ligands. One additional mole of PMcj causes loss of Cp from the metal. It is highly likely that the 77 -Cp complex is an intermediate in the reaction although it was not detected. When Cp ligands are found coordinated in arrangements other than the symmetric we sometimes refer to them as slipped ring systems. The rhenium reaction is an extreme example in which the ring has been induced to slip completely off the metal atom rf n Thus... 

Manganese and Rhenium.- Reactions of Mn and Re vapours with benzene in conjunction with PMe / cyclohexene, or an alkane, have afforded a variety of new complexes including (n-PhH)Mn(PMe )2H,... 

Rhenium hexafluoride is readily prepared by the direct interaction of purified elemental fluorine over hydrogen-reduced, 300 mesh (ca 48 pm) rhenium powder at 120°C. The reaction is exothermic and temperature rises rapidly. Failure to control the temperature may result in the formation of rhenium heptafluoride. The latter could be reduced to rhenium hexafluoride by heating with rhenium metal at 400°C. 

The composition of a reforming catalyst is dictated by the composition of the feedstock and the desired reformate. The catalysts used are principally platinum or platinum—rhenium on an alumina base. The purpose of platinum on the catalyst is to promote dehydrogenation and hydrogenation reactions. Nonplatinum catalysts are used in regenerative processes for feedstocks containing sulfur, although pretreatment (hydrodesulfurization) may permit platinum catalysts to be employed. 

Another synthesis of pyrogaHol is hydrolysis of cyclohexane-l,2,3-trione-l,3-dioxime derived from cyclohexanone and sodium nitrite (16). The dehydrogenation of cyclohexane-1,2,3-triol over platinum-group metal catalysts has been reported (17) (see Platinum-GROUP metals). Other catalysts, such as nickel, rhenium, and silver, have also been claimed for this reaction (18). 

Propylene oxide is also produced in Hquid-phase homogeneous oxidation reactions using various molybdenum-containing catalysts (209,210), cuprous oxide (211), rhenium compounds (212), or an organomonovalent gold(I) complex (213). Whereas gas-phase oxidation of propylene on silver catalysts results primarily in propylene oxide, water, and carbon dioxide as products, the Hquid-phase oxidation of propylene results in an array of oxidation products, such as propylene oxide, acrolein, propylene glycol, acetone, acetaldehyde, and others. 

Occurrence and Recovery. Rhenium is one of the least abundant of the naturally occurring elements. Various estimates of its abundance in Earth s cmst have been made. The most widely quoted figure is 0.027 atoms pet 10 atoms of silicon (0.05 ppm by wt) (3). However, this number, based on analyses for the most common rocks, ie, granites and basalts, has a high uncertainty. The abundance of rhenium in stony meteorites has been found to be approximately the same value. An average abundance in siderites is 0.5 ppm. In lunar materials, Re, when compared to Re, appears to be enriched by 1.4% to as much as 29%, relative to the terrestrial abundance. This may result from a nuclear reaction sequence beginning with neutron capture by tungsten-186, followed by p-decay of of a half-hfe of 24 h (4) (see Extraterrestrial materials). 

Also, ReS2 is the product formed by direct reaction of rhenium and sulfur. 

Salts of perrhenic acid may be obtained in acid—base reactions, and may include the tetrahedral ReO anion or the octahedral anion ReO , eg, in Ba (ReOg)2 [13598-09-9], Ammonium perrhenate and perrhenic acid, as well as rhenium metal, are sold by the primary suppHers of this element. 

Rhenium oxides have been studied as catalyst materials in oxidation reactions of sulfur dioxide to sulfur trioxide, sulfite to sulfate, and nitrite to nitrate. There has been no commercial development in this area. These compounds have also been used as catalysts for reductions, but appear not to have exceptional properties. Rhenium sulfide catalysts have been used for hydrogenations of organic compounds, including benzene and styrene, and for dehydrogenation of alcohols to give aldehydes (qv) and ketones (qv). The significant property of these catalyst systems is that they are not poisoned by sulfur compounds. 

Compounds of the formulas Re(CR]), ReO(CH3)4, Li2[Re2(CH3)g] [60975-25-9], Re02(CH3)3 [56090-011-8], and Re03CH3 [70197-13-6] have been prepared. The first two compounds were obtained from reaction of rhenium hahdes or oxyhahdes and methyllithium the last three were formed from the species by oxidation or reduction reactions. The use of these hydride and alkyl complexes as catalysts is under investigation. 

This reaction is cataly2ed in solution by complexes of tungsten, molybdenum, or rhenium in high oxidation states, eg, Re ". Examples of active catalysts are... 

Tme supported catalysts are not favored for this reaction, but it can be effected by the use of finely divided rhenium metal or rhenium (VI) oxide as well as hydrated mthenium (IV) oxide. 

Reduction of Carboxylic Acids to Alcohols. In addition to the nonsupported catalysts mentioned for the hydrogenation of amides to amines, mthenium and rhenium on alumina can be used to reduce carboxyHc acids to alcohols. The conditions for this reduction are somewhat more severe than for most other hydrogenation reactions and require higher temperatures, >150° C, and pressures, >5 MPa (725 psi) (55). Various solvents can be used including water. 

Reforming is the conversion primarily of naphthenes and alkanes to aromatics, but other reactions also occur under commercial conditions. Platinum or platinum/rhenium are the hydrogenation/ dehydrogenation component of the catalyst and alumina is the acid component responsible for skeletal rearrangements. 

Again, fluoro and oxo complexes of rhenium predominate. The reaction of KF and ReFe in an inert PTFE vessel yields pink K2[ReFs], the anion of which has a square-prismatic structure hydrolysis converts it to K[ReOFs]. 

SCHEME D Some reactions of rhenium carbonyl chlaide. 

Cp(CO)2Re(THF) forms the complex 105 upon reaction with thiophene (89JA8753, 910M2436). Similar species are known for 2- and 3-methyl-, 2,5-dimethyl, and tetramethylthiophene (91IC1417). Thiophene in 105 is S-coordi-nated, and the sulfur atom is pyramidal. Treatment of 105 with Fc2(CO)9 produces 106, where the thiophene ligand is bridge-coordinated via the sulfur atom to rhenium and four carbon atoms of the dienic system with iron (the coordination mode). The pyramidal nature of the sulfur atom is preserved. The -coordination of thiophene separates the dienic and sulfur counterparts of the ligand and decreases the TT-electron delocalization, which leads to the enhanced basicity of the sulfur atom. 

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