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Catalytic Reduction of 4-Nitrobenzoic Acid by cis-[Rh(CO)2(Amine)2](PF6) Complexes Under Water–Gas Shift Reaction Conditions: Kinetics Study

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Abstract

Rhodium(I) complexes of the type, cis-[Rh(CO)2(amine)2](PF6) where (amine = 3-picoline, 2-picoline, pyridine, 2,6-lutidina or 3,5-lutidine) dissolved in 80% aqueous amine solutions catalyzed the selective reduction of 4-nitrobenzoic acid to 4-aminobenzoic acid under CO atmosphere. The importance of these catalytic systems is their high chemo selectivity for the aromatic nitro group of the 4-nitrobenzoic acid with respect to the carboxylic group, allowing the production of the desired aromatic amine in high yields. The 4-aminobenzoic acid production depends on the nature of the coordinated amine. The Rh/3,5-lutidine system, the most active catalyst among tested, displays turnover frequencies for 4-aminobenzoic acid production of about 173 moles per mole Rh per day for [Rh] = 1 × 10−4 mol, [4-nitrobenzoic acid] = 3.82 × 10−3mol, 10 mL of 80% aqueous 3,5-lutidine, P(CO) = 0.9 atm at 100 °C. Analyses of kinetic results for the Rh/3,5-lutidine system show a first order dependence on 4-nitrobenzoic acid concentration, a non-linear dependence on CO pressure, a segmented Arrhenius plot and dependence on the nature of the reducing gas agent. These data are discussed in terms of a possible mechanism.

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Authors and Affiliations

  1. Centro de Investigaciones Químicas, Facultad de Ingeniería, Universidad de Carabobo, Valencia, Venezuela

    Celeste Fernández, Eduardo Lujano, Ursula Macias, Josseilin Marcano & Pablo J. Baricelli

  2. Centro de Investigación y Desarrollo de Radiofármacos, Facultad de Farmacia, Universidad Central de Venezuela, Caracas, Venezuela

    Clementina Longo

  3. Departamento de Química Aplicada, Facultad de Química y Biología, Universidad de Santiago de Chile, Casilla, 307-2 Santiago, Chile

    Sergio A. Moya

  4. Centro de Equilibrios en Solución, Escuela de Química, Facultad de Ciencias, Universidad Central de Venezuela, Caracas, Venezuela

    María G. Solórzano, Marisol C. Ortega & Alvaro J. Pardey

Authors
  1. Celeste Fernández
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  2. Eduardo Lujano
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  3. Ursula Macias
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  4. Josseilin Marcano
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  5. Pablo J. Baricelli
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  6. Clementina Longo
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  7. Sergio A. Moya
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  8. María G. Solórzano
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  9. Marisol C. Ortega
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  10. Alvaro J. Pardey
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Corresponding author

Correspondence to Pablo J. Baricelli.

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Fernández, C., Lujano, E., Macias, U. et al. Catalytic Reduction of 4-Nitrobenzoic Acid by cis-[Rh(CO)2(Amine)2](PF6) Complexes Under Water–Gas Shift Reaction Conditions: Kinetics Study. Catalysis Letters 95, 143–150 (2004). https://doi.org/10.1023/B:CATL.0000027287.78214.bf

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  • DOI: https://doi.org/10.1023/B:CATL.0000027287.78214.bf

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