Pressure ruthenium catalysis

This system shows an induction period of about six hours before constant activity is attained during which the Ru3(C0)12 undergoes complete conversion to another ruthenium carbonyl complex. In situ nmr studies suggest this species to be the HRu2(C0)e ion. Kinetic studies show complex rate profiles however, a key observation is that the catalysis rate is first order in Pco at low pressures (Pcohigher pressures. A catalysis scheme consistent with these observations is proposed. 

Research with an alkali-promoted (potassium or K2O) ruthenium catalyst has demonstrated that ammonia synthesis can be effected at lower temperatures and pressures than those required by the Haber process. As the price of energy increases, ruthenium catalysis might become increasingly important, because the energy-expensive compression process could be avoided. Another advantage of ruthenium if its diminished susceptibility to poisoning by H2O and CO. Ruthenium catalysts can carry out the direct synthesis of ammonia from N2, CO, and H2O ... 

The kinetics results of the batch reactor runs lead to the following qualitative observations At low CO pressures (less than about 1 atm) the catalysis appears to be first order in ruthenium over the range 0.018 M to 0.072 M and also in Pco as illustrated by the log Pco vs time plots of Fig. 2 and also shown by the method of initial rates. Changes in the sulfuric acid and water concentrations over the respective ranges 0.25 M to 2.0 M and 4 M to 12 M have relatively small effects on the catalysis rates, although the functionalities are complicated and show concave rate vs concentration curves with maximum rates... 

Solutions of ruthenium carbonyl complexes in acetic acid solvent under 340 atm of 1 1 H2/CO are stable at temperatures up to about 265°C (166). Reactions at higher temperatures can lead to the precipitation of ruthenium metal and the formation of hydrocarbon products. Bradley has found that soluble ruthenium carbonyl complexes are unstable toward metallization at 271°C under 272 atm of 3 2 H2/CO [109 atm CO partial pressure (165)]. Solutions under these conditions form both methanol and alkanes, products of homogeneous and heterogeneous catalysis, respectively. Reactions followed with time exhibited an increasing rate of alkane formation corresponding to the decreasing concentration of soluble ruthenium and methanol formation rate. Nevertheless, solutions at temperatures as high as 290°C appear to be stable under 1300 atm of 3 2 H2/CO. 

The observed ratio of [HRu3(CO)n] to [Ru(CO)3I3] in solutions after catalysis is sometimes found to vary from the 2 1 ratio shown by (59). This may be expected if acids or bases (e.g., a basic solvent) are involved in oxidation or reduction processes, which can interconvert the two such equilibria can change with pressure (193). Nevertheless, these two species are normally observed to be stable under catalytic conditions, and a combination of the two is found to provide the optimum catalytic rates (e.g., see Fig. 21). Catalyst solutions derived from nonhalide salt promoters are presumed to contain [HRu3(CO)n] and an oxidized ruthenium species analogous to [Ru(CO)3I3]-, although no detailed studies of such systems have been reported. 

The first transition metal catalysis using BINAP-ruthenium complex in homogeneous phase for enantioselective hydrogenation of P-ketoesters was developed by Noyori and co-workers [31]. Genet and co-workers described a general synthesis of chiral diphosphine ruthenium(II) catalysts from commercially available (COD)Ru(2-methylallyl)2 [32]. These complexes preformed or prepared in situ have been found to be very efficient homogeneous catalysts for asymmetric hydrogenation of various substrates such as P-ketoesters at atmospheric pressure and at room temperature [33]. 

As is showm in Figure 2, methane is formed over nickel and ruthenium catalysts, especially at low pressures (atmospheric up to 10 bar) and elevated temperatures. Paraffins and olefins are produced over nickel and cobalt catalysis at mild temperatures (< 200 0) and pressures of I -10 bar. With iron catalysts, olefins,parafllns.and minor amounts of alcohols are formed at medium pressures (10 100 bar) and temperatures of 210--340 C. Ruthenium catalysts give, at elevated pressures (150-1000 bar) and low temperatures (100-180 C), poly methylene with a molecular weiglii of up to I 000000. This polymer has similar properties as Ziegler-type low pressure polyethylene. 

The carbonyl [Ru3(CO),2] is a good cocatalyst for the low pressure hydroformylation of internal alkenes using the classic rhodium phosphine [HRh(CO)(PPh3),] system in the presence of an excess of triphenylphosphine (P/Rh = 200) (22). Starting from a mixture of hex-2- and hex-3-ene, the addition of [Ru3(CO),2l (Rh/Ru = 1/1) increased both the reaction rate and the n/iso ratio of heptanals. More recently, Poilblanc and coworkers (23) have prepared a mixed ruthenium-rhodium complex formulated as [CIRh(/i-CO)(//-dppm)2Ru(CO)2] (dppm is Ph2PCH2PPh2). This species shows catalytic activity in the hydroformylation of pent-l-ene at 40 bar (H2/C0= 1/1) and 75°C. Conversion to hexanals was 90% in 24 hours and the linearity reached 70%. No further report has appeared to determine the role of the two metals in this catalysis. 

Our studies have focussed largely on the catalysis of the shift reaction by ruthenium carbonyl and by the ruthenium carbonyl/iron carbonyl mixtures in the presence of organic amines under low pressures of CO. Representative studies are indicated in Table II where it is notable that ruthenium alone is a considerably better catalyst than is iron alone. Among the ruthenium systems, pyridine solutions are somewhat more... 

The preparation of ethylene glycol directly from synthesis gas via homogeneous rhodium (14-20), ruthenium (21-26), and cobalt (27-30) catalysis has generally been limited by the high pressures necessary to effect reaction and the modest turnover frequencies. We have demonstrated the preparation of ethylene glycol and its monoalkyl ether derivatives from CO/H2 (eq. 1) using ruthenium or a Ru-Rh catalyst combination dispersed in a low-melting quaternary phosphonium or ammonium salt such as tetrabutylphosphonium bromide. Monohydric alkanols are the major by-products data in Table 1 illustrate typical preparations. The important features of this catalysis are ... 

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