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The acid-aided heterobimetallic ruthenium-cobalt catalytic system for the reductive hydroformylation with carbon dioxide was established. Various alkenes, including waste from biomass and petroleum industry, could be upgraded to valuable alcohols with this protocol. Acid-promoted reverse water-gas shift (RWGS), thereby accelerating the hydroformylative synthesis of alcohol. The theoretical computations revealed that acid promoted RWGS by facilitating the dehydroxylation of ruthenium hydroxy carbonyl intermediate.

The complex [RhH(PEt3)3] catalysed the hydroformylation of hex-1-ene to heptanal and 2-methylhexanal in toluene, but heptanol and 2-methylhexanol were significant products in tetrahydrofuran especially over long reaction times (16 h). In protic solvents only alcohols were produced even after short reaction times. The reactions are very rapid and also occur readily with alkenes such as hex-2-ene, propene, ethene, styrene and 3,3-dimethylbutene. The highest rates observed are for ethene (54 000 turnovers h-1) and the products in all cases are alcohols. Other phosphines containing primary alkyl groups also produced alcohols, but in contrast reactions in ethanol using rhodium complexes containing PPh3, PPh2Et, PPhEt2 or PPri3 produced significant amounts of aldehydes and/or acetals whilst Me2PCH2CH2PMe2 inhibited the reaction. The NMR studies showed that species present in equilibrium in ethanol solution are [RhH(CO)(PEt3)3], [RhH(CO)2(PEt3)2], [Rh2(CO)4(PEt3)4], [Rh2(CO)2(PEt3)6] and PEt3 but that [RhH(CO)(PEt3)3] predominates under the catalytic conditions. Reactions carried out under D2-CO in EtOH produced 90% BuCHDCH2CD2OH/D and 10% BuCHDCH2CHDOH/D but hydrogenation of heptanal under the same conditions gave a mixture of C6H13CHDOH/D (39%) and C6H13CH2OH/D (61%). These results are interpreted to indicate that the alcohols produced from hex-1-ene are primary reaction products and not produced via intermediate aldehydes. A new mechanism for this direct hydrocarbonylation is proposed in which the key acyl intermediate becomes protonated by the alcoholic solvent because of the high electron density it bears as a result of the presence of the electron-donating trialkylphosphines. Oxidative addition of H2 followed by two H-atom transfers leads directly to the alcohol. High pressure NMR studies showed that [Rh{C(O...HOEt)Et}(CO)2(PEt3)2] is present during catalytic hydrocarbonylation of ethene in ethanol. Two different cycles are proposed to explain the products obtained from the catalytic reaction of heptanal with D2-CO. Again, protonation, this time of the metal, appears to be important.

In the presence of methanesulfonic acid the platinum(0) complex catalyses the hydroformylation of various olefins.In some cases there is quite good chemoselectivity and high regioselectivity towards n-aldehyde.