Cobalt hydrocarbonyl catalyst preparation

It has been observed that rapid isomerization accompanies the cobalt carbonyl-catalyzed hydrosilation of olefins (18). The reaction of equimolar amounts of a trisubstituted silane and dicobalt octacarbonyl has been shown to result in the formation of cobalt hydrocarbonyl (cf. Section IV). A very effective isomerization catalyst may be prepared by treatment of a solution of Co2(CO)8 in olefin ( 0.01 M) with a silicon hydride in sufficient quantity to slightly exceed the cobalt carbonyl concentration. 

The hydroformylation of alkenes generally has been considered to be an industrial reaction unavailable to a laboratory scale process. Usually bench chemists are neither willing nor able to carry out such a reaction, particularly at the high pressures (200 bar) necessary for the hydrocarbonylation reactions utilizing a cobalt catalyst. (Most of the previous literature reports pressures in atmospheres or pounds per square inch. All pressures in this chapter are reported in bars (SI) the relationship is 14.696 p.s.i. = 1 atm = 101 325 Pa = 1.013 25 bar.) However, hydroformylation reactions with rhodium require much lower pressures and related carbonylation reactions can be carried out at 1-10 bar. Furthermore, pressure equipment is available from a variety of suppliers and costs less than a routine IR instrument. Provided a suitable pressure room is available, even the high pressure reactions can be carried out safely and easily. The hydroformylation of cyclohexene to cyclohexanecarbaldehyde using a rhodium catalyst is an Organic Syntheses preparation (see Section 4.5.2.5). 

The treatment of a cobalt(II) salt with synthesis gas generates sequentially Co2(CO)8 then HCo(CO>4. This catalyst is generated only at 120-140 C for the carbonylation to proceed smoothly 200-300 bar is required to stabilize the catalyst. If the hydridocobalt catalyst is prepared separately and then introduced into the reaction, temperatures as low as 90 C can be used for the hydrocarbonylation. An important consideration in industrial reactions is the normal to branched nib ratio to give the desired straight chain aldehyde, the hydridocobalt catalyst providing an nib ratio of -4 in the hydroformylation of propene under the lower temperature conditions. This catalyst will stoichiometrically hydroformylate 1-alkenes under ambient conditions. 

Cobaltcarbonyls are used as catalysts for carbonylations such as hydroformylation (0x0 reaction), hydrocarbonylation and amidocarbonylation [70a]. Hydroformylation is the reaction of preparing aliphatic aldehydes in which carbon number is increased by one [46]. Especially, butylaldehyde has been industrially produced largely from propylene butylaldehyde is used as a raw material for butanol and 2-ethylhexanol, etc. Cobalt and rhodium compounds are used for their catalysts. The reactivity of cobalt catalysts is lower than that of rhodium catalysts. However, more linear products of the reaction shown in eq. (17.27) are obtained. The ratio of... 

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