Abstract
The water gas shift reaction (CO + H2O = CO2+ H2) is catalyzed by aqueous metal carbonyl systems derived from simple mononuclear carbonyls such as Fe(CO)5 and M(CO)6 (M = Cr, Mo, and W) and bases in the 140–200 °C temperature range. The water gas shift reaction in a basic methanol-water solution containing Fe(CO)5 is first order in [Fe(CO)5], zero order in [CO], and essentially independent of base concentration and appears to involve an associative mechanism with a metallocarboxylate intermediate [(CO)4Fe-CO2H]−. The water gas shift reactions using M(CO)6 as catalyst precursors are first order in [M(CO)6], inverse first order in [CO], and first order in [HCO2 −] and appear to involve a dissociative mechanism with formatometallate intermediates [(CO)5M-OCHO]−.
The Reppe hydroformylation of ethylene to produce propionaldehyde and 1-propanol in basic solutions containing Fe(CO)5 occurs at 110–140 °C. This reaction is second order in [Fe(CO)5], first order in [C2H4] up to a saturation pressure >1.5 MPa, and inhibited by [CO]. These experimental results suggest a mechanism where the rate-determining step involves a binuclear iron carbonyl intermediate. The substitution of Et3N for NaOH as the base facilitates the reduction of propionaldehyde to 1-propanol but results in a slower rate for the overall reaction.
The homogeneous photocatalytic decomposition of the formate ion to H2 and CO2 in the presence of Cr(CO)6 appears to be closely related to the water gas shift reaction. The rate of H2 production from the formate ion exhibits saturation kinetics in the formate ion and is inhibited by added pyridine. The infrared spectra of the catalyst solutions indicate an LCr(CO)5 intermediate. Photolysis of the Cr(CO)6/formate system in aqueous methanol in the presence of an aldehyde RCHO (R =n-heptyl,p-tolyl, andp-anisyl) results in catalytic hydrogenation of the aldehyde to the corresponding alcohol RCH2OH by the formate ion. Detailed kinetic studies onp-tolualdehyde hydrogenation by this method indicates saturation kinetics in formate ion, autoinhibition by thep-tolualdehyde, and a threshold effect for Cr(CO)6 at concentrations >0.004 mol L−1. The presence of an aldehyde can interrupt the water gas shift catalytic cycle by interception of an HCr(CO)5 − intermediate by the aldehyde.
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References
C. L. Thomas,Catalytic Processes and Proven Catalysts, Academic Press, New York, 1970.
R. M. Laine, R. C. Rinker, and P. C. Ford,J. Am. Chem. Soc., 1977,99, 252.
H. Kang, C. H. Mauldin, T. Cole, W. Slegier, K. Cann, and R. Pettit,J. Am. Chem. Soc., 1977,99, 8323.
C.-H. Cheng, D. E. Hendricksen, and R. Eisenberg,J. Am. Chem. Soc., 1977,99, 2791.
C. H. Cheng and R. Eisenberg,J. Am. Chem. Soc., 1978,100, 5968.
T. Yoshida, Y. Ueda, and S. Otsuka,J. Am. Chem. Soc., 1978,100, 3941.
R. B. King, C. C. Frazier, R. M. Hanes, and A. D. King, Jr.,J. Am. Chem. Soc., 1978,100, 2925.
A. D. King, Jr., R. B. King, and D. B. Yang,J. Am. Chem. Soc., 1980,102, 1028.
A. D. King, Jr., R. B. King, and D. B. Yang,J. Am. Chem. Soc., 1981,103, 2699.
R. Massoudi, J. H. Kim, R. B. King, and A. D. King, Jr.,J. Am. Chem. Soc., 1987,109, 7428.
D. E. Linn, Jr., R. B. King, and A. D. King, Jr.,J. Mol. Catal., 1993,80, 151.
D. E. Linn, Jr., R. B. King, and A. D. King, Jr.,J. Mol. Catal., 1993,80, 165.
W. Reppe and H. Vetter,Liebigs Ann. Chem., 1953,582, 133.
A. D. King, Jr., R. B. King, and E. L. Sailers, III,J. Am. Chem. Soc., 1981,103, 1867.
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Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1533–1539, September, 1994.
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King, R.B., King, A.D. Metal carbonyl catalysis of carbon monoxide and formate reactions. Russ Chem Bull 43, 1445–1450 (1994). https://doi.org/10.1007/BF00697123
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DOI: https://doi.org/10.1007/BF00697123