Described are quantitative studies of the CO/H2O reduction of various nitroaromatics to the respective anilines under water-gas shift reaction (WGSR) conditions catalyzed by solutions of RhCl3 in aqueous amines. The most active media were aqueous tetramethylethylenediamine and 2-picoline solutions. The reduction rates exhibited first-order dependence on P(CO) over the 0.3-1.5 atm range, but turnover frequencies decreased as the total rhodium concentration increased over the range 5-40 mM. The latter behavior was interpreted in terms of the coexistence of mononuclear and polynuclear Rh species in the system, the mononuclear being the more catalytically active. Relative shift reaction and reduction rates indicate that the nitroaromatics must be reduced by an independent catalytic cycle rather than by the WGSR produced H-2. (C) 2003 Elsevier Science B.V. All rights reserved.