Reactions Involving CO and

The catalytic synthesis of hydrocarbons from syngas is also represented by the Fischer-Tropsch process (141). 

A particularly broad potential for application in syngas reactions is shown by ruthenium carbonyl clusters. Iodide promoters seem to favor ethylene glycol (155,156) the formation of [HRu3(CO),]- and [Ru(CO)3I3]- was observed under the catalytic conditions. These species possibly have a synergistic effect on the catalytic process. Imidazole promoters have been found to increase the catalytic activity for both methanol and ethylene glycol formation (158-160). Quaternary phosphonium salt melts have been used as solvents in these cases the anion [HRu3(CO)u] was detected in the mixture (169). Cobalt iodide as cocatalyst in molten [PBu4]Br directs the catalytic synthesis toward acetic add (163). With 

Hydrogenation of Carbon Monoxide Catalyzed by Various Transition Metal Clusters 

Catalyst Products (%) (bar Hj/bar CO) Time turnover Remarks References 

Ru3(CO)12 Methyl acetate (99), ethylene glycol Acetic acid, 260°C 2 hr 177 (154) 

RU3(C0) 2 Methanol (62), methyl formate (22), ethanol (1), ethylene glycol formate (1), methyl acetate (1) Af-Methylpyrrolidone, 230 C (1000/1000) 2hr NG Conversion 25% (148,149) 

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A zeolite catalyst operated at 1 atm and 325-500 K is so active that the reaction approaches equilibrium. Suppose that stack gas having the equilibrium composition calculated in Example 7.17 is cooled to 500 K. Ignore any reactions involving CO and CO2. Assume the power plant burns methane to produce electric power with an overall efficiency of 70%. How much ammonia is required per kilowatt-hour (kWh) in order to reduce NO , emissions by a factor of 10, and how much will the purchased ammonia add to the cost of electricity. Obtain the cost of tank car quantities of anhydrous ammonia from the Chemical Market Reporter or from the web. 

As noted earlier HCo(CO)4 and H2Fe(CO)4 were the first known hydrides. Carbonyl hydrides and carbonylate anions have been intensively studied in part because they are intermediates in many metal catalyzed reactions involving CO and H2. The structure of HMn(CO)5 is shown in Fig. 2-7. 

Strictly related to catalytic reactions involving CO and H20 are reactions in which CO and alcohols, ROH, or CO and amines, R2NH, are used as building blocks. The catalytic addition of carbon monoxide and an alcohol to an olefin yields carboxylic esters (hydroesterification). Thus, the synthesis of methyl propionate from ethylene, CO, and methanol using a catalytic system composed of Ru3(CO)u and [PPh4]I (190°C, 20 bar C2H4, 45 bar CO, 2.5 hr, yield 74%, CT 1000) has been reported (323) ... 

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