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Effect of carboxylic acids on the yield and selectivity of the hydroformylation of hex-1-ene catalyzed by [Rh(acac)(CO)(PPh3)].

Autorzy

Ewa Mieczyńska

Anna M. Trzeciak

Józef J. Ziółkowski

Rok wydania

1993

Czasopismo

Journal of Molecular Catalysis

Numer woluminu

80

Strony

189-200

DOI

10.1016/0304-5102(93)85077-7

Kolekcja

Naukowa

Język

Angielski

Typ publikacji

Artykuł

Streszczenie

The effect of the carboxylic acids RCO2H (RC2H5, C6H5, m-ClC6H4, p-NO2C6H4 and o-HOC6H4) on the hydroformylation of hex-1-ene catalysed by Rh(acac) (CO) (PPh3) (1) have been studied. The decrease of the rate of hydroformylation compared with a carboxylic acid-free system was observed. The inhibiting influence of carboxylic acids is stronger in reactions proceeding in the presence of free phosphine (e.g. (1)/[RCO2H+PPh3]) where not only the reaction rate, but also hex-1-ene conversion decrease. The inhibiting effect of carboxylic acids may be explained by partial elimination of catalytically active forms of the general formula HRh(CO)x(PPh3)y by the reaction of HRh(CO)x(PPh3)y in the presence of RCO2H/PPh3 and H2/CO to give Rh(RCO2) (CO) (PPh3)2. The equilibrium of this reaction depends mainly on the concentrations of the H+ ions and that of free phosphine. Several new rhodium complexes were formed in the reaction of (1) with RCO2H, e.g., [Rh(RCO2) (CO) (PPh3)]2, [Rh(RCO2) (CO)2(PPh3)], [Rh(RCO2) (CO) (PPh3)2], [Rh(RCO2) (CO)2]2, have been isolated and used as hydroformylation reaction catalysts. The structures of Rh(acac) (HOC6H4CO2)2(PPh3) (H2O) and [Rh(HOC6H4CO2) (COD)]2 have been determined by X-ray diffraction studies.

Adres publiczny

https://doi.org/10.1016/0304-5102(93)85077-7

Strona internetowa wydawcy

http://www.elsevier.com

Podobne publikacje
1992

Hydroformylation and isomerization of hex-1-ene catalyzed by [Rh(acac)(CO)(PPh3)]: effect of modifying ligands.

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1990

Hex-1-ene hydroformylation catalyzed by Rh(acac){P(OPh)3}3 modified with amines, formation of reactive HRh(CO){P(OPh)3}3 and unreactive Rh4(CO)8{P(OPh)3}4 species.

Trzeciak Anna M.

1991

Effect of modifying ligands (P(OPh)3, PPh3, dppe and cp2Zr(CH2PPh2)2) on hex-1-ene hydroformylation catalyzed by [HRh{P(OPh)3}4] and [HRh(CO) {P(OPh)3}3].

Trzeciak Anna M., Ziółkowski Józef J., Choukroun R.