Cobalt carbonyl and rhodium complexes catalyse the hydroformylation of formaldehyde and ethylene oxide to give hydroxyacetaldehyde and 3-hydroxypropanal, which can then be hydrogenated to ethylene glycol and propane-1,3-diol, respectively. The reactions work best when the solvent is basic (such as pyridine).
In the case of dicobalt octacarbonyl or Co(CO) as a catalyst, pentan-3-one can arise from ethene and CO, in the absence of hydrogen. A proposed intermediate is the ethylene-propionyl species [CHC(O)Co(CO)(ethene)] which undergoes a migratory insertion to form [CHCOCHCHCo(CO)]. The required hydrogen arises from the water shift reaction. For details, see
If the water shift reaction is not operative, the reaction affords a polymer containing alternating carbon monoxide and ethylene units. Such aliphatic polyketones are more conventionally prepared using palladium catalysts.
Functionalized olefins such as allyl alcohol can be hydroformylated. The target product 1,4-butanediol and its isomer is obtained with isomerization free catalysts such as rhodium-triphenylphosphine complexes. The use of the cobalt complex leads by isomerization of the double bond to n-propanal. The hydroformylation of alkenyl ethers and alkenyl esters occurs usually in the α-position to the ether or ester function.
The hydroformylation of acrylic acid and methacrylic acid in the rhodium-catalyzed process leads to the Markovnikov product in the first step. By variation of the reaction conditions the reaction can be directed to different products. A high reaction temperature and low carbon monoxide pressure favors the isomerization of the Markovnikov product to the thermodynamically more stable β-isomer, which leads to the n-aldehyde. Low temperatures and high carbon monoxide pressure and an excess of phosphine, which blocks free coordination sites, can lead to faster hydroformylation in the α-position to the ester group and suppress the isomerization.