Advances in Organometallic Chemistry, Vol. 17: Catalysis and by F.G.A. Stone, Robert West (Eds.)

By F.G.A. Stone, Robert West (Eds.)

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Extra info for Advances in Organometallic Chemistry, Vol. 17: Catalysis and Organic Syntheses

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The amount of cross-linking was found to be critical: too little gave a soluble polymer, while too much gave an intractable material which absorbed little metal. Cobalt was used as t h e catalyst, and the reaction was conducted at 15O0-2O0"C and 2000-3000 psi of lil H,/CO. 48 ROY L. PRUETT It was concluded that in this case an equilibrium existed which gave 100 ppm of soluble cobalt at reaction temperature. The polymer support acted as a reservoir for furnishing soluble metal at reaction temperature and reabsorbing it after completion (about 10 ppm in the product after cooling to ambient temperature).

Results are detailed in Tables V and VI. The percent of n-aldehyde rose rapidly as the carbon monoxide partial pressure was increased up to 30-40 atm CO; further increase had little effect. 1-Pentene clearly gave a higher percentage of straight-chain aldehyde than 2-pentene, but the difference was insignificant in the lower P c o experiments. The hydrogen partial pressure has a small but reproducible effect on the hydroformylation product composition. The direction of the change found was the same as for carbon monoxide partial pressures: the experiments gave higher percentages of n-aldehyde.

Linear isomer. However, later work suggests that these results may have been artifacts caused by high reaction rates. Both high temperatures and high catalyst concentration increase the rate of aldehyde formation and probably caused a depletion in dissolved carbon monoxide. This would have the same apparent effect as a lower partial pressure of carbon monoxide. Pino et a l . 6%. They also found that, provided the reaction rate was controlled by varying the concentration of olefin and of catalyst, the product composition varied only slightly as a function of either temperature or catalyst concentration.

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