Superoxometal-catalyzed co-oxidation of alcohols and nitrous acid with molecular oxygen

Abstract

A superoxochromium(III) ion, CraqOO2+, acts as a catalyst for the co-oxidation of alcohols and nitrous acid with molecular oxygen according to the stoichiometry: CH3OH + HNO2 + O2 + CH2O + NO3- + H2O + H+. The kinetics are second order in [HNO2] and independent of the concentrations of the superoxochromium catalyst, substrate, and O2. The proposed mechanism features the disproportionation of HNO2 to NO and NO2, both of which react rapidly with CraqOO2+. The CraqOO2+/NO reaction generates another equivalent of NO2 and a mole of CraqO2+, the active oxidant. The two-electron oxidation of the alcohol by CraqO2+ produces Craq2+, which reacts rapidly with O2 to regenerate the catalyst, CraqOO2+. The NO2/CraqOO2+ reaction yields the peroxynitrato complex, CraqOONO22+, in a dead-end equilibrium process that has no effect on the catalytic reaction. The disproportionation of NO2 yields the final nitrogen-containing product, NO3-, and regenerates an equivalent of HNO2. Under a fixed set of conditions, the relative catalytic efficiency (CE) of CraqOO2+ decreases as its concentration increases owing to the competition between O2 and CraqOO2+ for the intermediate Craq2+. © 2003 Elsevier Science B.V. All rights reserved.