Rhodium catalysts activation

The initial steep rise can be attributed simply to activation of the catalyst precursor. The amount of base corresponds approximately to one equivalent of KOH for the ruthenium catalyst and two equivalents for the rhodium catalyst. Activation could result from hydroxide attack as in (5) and (6) for rhodium and (10) for ruthenium ... 

As indicated above, hydrogen has a definite influence upon the catalyst. This is manifest in several ways, (a) Small amounts of hydrogen effectively keep this same rhodium catalyst active and in solution in the carbonylation of methyl acetate. (b) The rates of... 

Less reactive olefins such as 2,2-dialkyl-1-alkenes are hydroformylated at much higher rates than those achieved with TPP-modified rhodium catalysts. Activities of 15 000 mol (aldehyde)/mol (Rh) h have been reported (90 °C, 1-3 MPa) [39]. 1-Alkenes are converted with even higher rates (activity = 160000 mol/mol h). At these high rates the reaction becomes mass-transfer limited. The lack of CO dissolved in the liquid layer leads to formation of unsaturated rhodium species which rapidly isomerize the olefin. The n/i ratio obtained is therefore low (20-30% linear product). The stmcture of hydrido-rhodium diphosphite complexes was investigated in detail by NMR spectroscopy [41]. BASF reported the hydroformylation of methyl 3-pentenecarboxylate with Rh(CO)2(acac) and 3 as a ligand. Methyl 5-formalvalerate was formed with 72 % selectivity [42]. 

Similar activation takes place in the carbonylation of dimethyl ether to methyl acetate in superacidic solution. Whereas acetic acid and acetates are made nearly exclusively using Wilkinson s rhodium catalyst, a sensitive system necessitating carefully controlled conditions and use of large amounts of the expensive rhodium triphenylphosphine complex, ready superacidic carbonylation of dimethyl ether has significant advantages. 

Rhodium Ca.ta.lysts. Rhodium carbonyl catalysts for olefin hydroformylation are more active than cobalt carbonyls and can be appHed at lower temperatures and pressures (14). Rhodium hydrocarbonyl [75506-18-2] HRh(CO)4, results in lower -butyraldehyde [123-72-8] to isobutyraldehyde [78-84-2] ratios from propylene [115-07-17, C H, than does cobalt hydrocarbonyl, ie, 50/50 vs 80/20. Ligand-modified rhodium catalysts, HRh(CO)2L2 or HRh(CO)L2, afford /iso-ratios as high as 92/8 the ligand is generally a tertiary phosphine. The rhodium catalyst process was developed joindy by Union Carbide Chemicals, Johnson-Matthey, and Davy Powergas and has been Hcensed to several companies. It is particulady suited to propylene conversion to -butyraldehyde for 2-ethylhexanol production in that by-product isobutyraldehyde is minimized. 

Other Rhodium Processes. Unmodified rhodium catalysts, eg, 1 14(00)22 [19584-30-6] have high hydroformylation activity but low selectivity to normal aldehydes. 

Efficient enantioselective asymmetric hydrogenation of prochiral ketones and olefins has been accompHshed under mild reaction conditions at low (0.01— 0.001 mol %) catalyst concentrations using rhodium catalysts containing chiral ligands (140,141). Practical synthesis of several optically active natural... 

The most common oxidation states, corresponding electronic configurations, and coordination geometries of iridium are +1 (t5 ) usually square plane although some five-coordinate complexes are known, and +3 (t7 ) and +4 (t5 ), both octahedral. Compounds ia every oxidation state between —1 and +6 (<5 ) are known. Iridium compounds are used primarily to model more active rhodium catalysts. 

Conventional triorganophosphite ligands, such as triphenylphosphite, form highly active hydroformylation catalysts (95—99) however, they suffer from poor durabiUty because of decomposition. Diorganophosphite-modified rhodium catalysts (94,100,101), have overcome this stabiUty deficiency and provide a low pressure, rhodium catalyzed process for the hydroformylation of low reactivity olefins, thus making lower cost amyl alcohols from butenes readily accessible. The new diorganophosphite-modified rhodium catalysts increase hydroformylation rates by more than 100 times and provide selectivities not available with standard phosphine catalysts. For example, hydroformylation of 2-butene with l,l -biphenyl-2,2 -diyl... 

A synthesis of optically active citroneUal uses myrcene (7), which is produced from P-piaene. Reaction of diethylamine with myrcene gives A/,A/-diethylgeranyl- and nerylamines. Treatment of the aHyUc amines with a homogeneous chiral rhodium catalyst causes isomerization and also induces asymmetry to give the chiral enamines, which can be readily hydrolyzed to (+)-citroneUal (151). 

With Unsaturated Compounds. The reaction of unsaturated organic compounds with carbon monoxide and molecules containing an active hydrogen atom leads to a variety of interesting organic products. The hydroformylation reaction is the most important member of this class of reactions. When the hydroformylation reaction of ethylene takes place in an aqueous medium, diethyl ketone [96-22-0] is obtained as the principal product instead of propionaldehyde [123-38-6] (59). Ethylene, carbon monoxide, and water also yield propionic acid [79-09-4] under mild conditions (448—468 K and 3—7 MPa or 30—70 atm) using cobalt or rhodium catalysts containing bromide or iodide (60,61). 

Two classes of metals have been examined for potential use as catalytic materials for automobile exhaust control. These consist of some of the transitional base metal series, for instance, cobalt, copper, chromium, nickel, manganese, and vanadium and the precious metal series consisting of platinum [7440-06-4], Pt palladium [7440-05-3], Pd rhodium [7440-16-6], Rh iridium, [7439-88-5], Ir and mthenium [7440-18-8], Ru. Specific catalyst activities are shown in Table 3. 

The rhodium catalyst (46 mg) is dissolved in acetone (10 ml) in a microhydrogenation apparatus which is then flushed three times with deuterium gas. After stirring the solution in an atmosphere of deuterium for about 1 hr the deuterium uptake ceases and constant pressure is attained. 5a-Cholest-2-ene (136, 19.5 mg) is added and the stirring continued until deuterium uptake ceases (about 3/4 hr). The solvent is evaporated to dryness and the residue is extracted with hexane and the resulting solution filtered through a small alumina column (3 g, activity 111). Evaporation of the hexane gives 2, 3 -d2-5oc-cholestane (137) 18 mg, 92% mp 78-79° isotope composition 94%d2,5%d, andl%do. ... 

Figure 5.2-1 Stabilization of the active rhodium catalyst by addition of the ionic liquid...

Such a complex, cw-Rh(CO)2I2, is the active species in the Monsanto process for low-pressure carbonylation of methanol to ethanoic acid. The reaction is first order in iodomethane and in the rhodium catalyst the rate-determining step is oxidative addition between these followed by... 

GP 8[ [R 7] Rhodium catalysts generally show no pronoimced activation phase as given for other catalysts in other reactions [3]. In the first 4 h of operation, methane conversion and hydrogen selectivity increases by only a few percent. After this short and non-pronounced formation phase, no significant changes in activity were determined in the experimental runs for more than 200 h. 

Noble metal loss of about 0.1 wt.-% of the honeycomb rhodium catalyst was observed during 200 h of operation similar effects are also known in commercial ammonia combustion processes [3]. This did not lead to a decrease in catalyst activity as rhodium was the only construction material. 

The equilibrium values are not reached at a rhodium catalyst on a micro structured reactor within the limits of the experimental conditions and the constructional constraints [3]. As possible explanations post-catalytic reactions at lower temperatures or, more likely, insufficient catalyst activity concerning the short residence times are seen. 

The use of rhodium catalysts for the synthesis of a-amino acids by asymmetric hydrogenation of V-acyl dehydro amino acids, frequently in combination with the use of a biocatalyst to upgrade the enantioselectivity and cleave the acyl group which acts as a secondary binding site for the catalyst, has been well-documented. While DuPhos and BPE derived catalysts are suitable for a broad array of dehydroamino acid substrates, a particular challenge posed by a hydrogenation approach to 3,3-diphenylalanine is that the olefin substrate is tetra-substituted and therefore would be expected to have a much lower activity compared to substrates which have been previously examined. 

As expected initial examination of the hydrogenation of this substrate revealed its relatively low activity compared to dehydroamino acids that provide 3-aryl-a-amino acids. By carrying out the hydrogenation at an elevated temperature, however, the inherent low activity could be overcome. A screen of the Dowpharma catalyst collection at S/C 100 revealed that several rhodium catalysts provided good conversion and enantioselectivity while low activity and selectivity was observed with several ruthenium and iridium catalysts. Examination of rate data identified [(l )-PhanePhos Rh (COD)]Bp4 as the most active catalyst with a rate approximately... 

Batch Experimental Apparatus and Methods. The activity of the rhodium catalyst was tested in a 125 mL reactor with a pressure rating of 3000 psi at 350°C and a pressure relief valve that is rated for 1500-2200 psi. If the pressure valve releases, the gaseous contents of the autoclave are safely vented through a 1/4" stainless steel line and the liquid/vapor content in the autoclave is collected in a metal container and the vapor vented out through the hood. The reactor was heated in a silicone oil bath with a digitally controlled heat/stir plate. 

In order to improve the selectivity toward the formation of 1,3-PDO, we studied the influence of metal salt additives. While the addition of calcium or copper salts exhibited a moderate influence, the presence of iron salts played a significant role on the rate and selectivity of the reaction (Figure 35.1). The metal additives reduced noticeably the activity of the rhodium catalysts suggesting that they acted as a surface poison, but they modified the selectivity of the glycerol hydrogenolysis, probably through selective diol chelation. 

Wender et al. reported a [5+2] cycloaddition in water by using a water-soluble rhodium catalyst having a bidentate phosphine ligand to give a 7-membered ring product (Eq. 4.69). This water-soluble catalyst was reused eight times without any significant loss in catalytic activity.133... 

In 1968 Wilkinson discovered that phosphine-modified rhodium complexes display a significantly higher activity and chemoselectivity compared to the first generation cobalt catalyst [29]. Since this time ligand modification of the rhodium catalyst system has been the method of choice in order to influence catalyst activity and selectivity [10]. 

Recently, a new class of phosphabarrelene/rhodium catalysts has been developed, which for the first time allows for hydroformylation of internal alkenes with very high activity and which proceeds essentially free of alkene isomerization [36-38]. Two examples, results of hydroformylation of an acyclic and a cyclic internal alkene substrate, are depicted in Scheme 2. 

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