Journal of the American Chemical Society, Vol.119, No.7, 1668-1675, 1997
Mechanism of Nitrous-Oxide Formation by Metal-Catalyzed Reduction of Nitric-Oxide in Aqueous-Solution
Kinetics data were collected for the palladium-catalyzed reduction of nitric oxide (NO) to nitrous oxide (N2O) with cuprous chloride reductant in 2 M hydrochloric acid (2NO + 2CuCl + 2HCl --> N2O + 2CuCl(2) + H2O). The rate-determining step was first order in the palladium concentration and NO partial pressure. The cuprous chloride dependence was first order below 0.1 M; at higher concentrations saturation kinetics were observed. The rate of reaction was independent of H+ and Cl- concentrations. Kinetics results were consistent with the initial, reversible attack (k(1)/k(-1)) of free NO on the bound nitrosyl of [PdCl3NO](2-) yielding [PdCl3(N2O2)](2-), which is then reduced by Cu(I) (k(2)) to generate products and recycle the palladium. A k(1) value of (6.0 +/- 0.4) x 10(-6) (P-NO)(-1) s(-1) at 20 degrees C was calculated, with a k(-1)/k(2) ratio of 0.116 +/- 0.004 M. Rate measurements show that NO reduction by Cu(I) is the rate-limiting step in the Wacker-style catalysis of the CO + 2NO --> CO2 + N2O reaction. The current mechanism resembles the nitric oxide reductase activities of cytochrome c oxidases, which proceed by Cu(I) reduction of a heme bound nitrosyl, and cytochrome P450nor.
Keywords:CYTOCHROME-C-OXIDASE;CARBON-MONOXIDE;FUSARIUM-OXYSPORUM;COPPER PROTEINS;COMPLEXES;PALLADIUM(II);OXIDATION;NO;CHEMISTRY;KINETICS