V. Raab et al., Ligand effects in the copper catalyzed aerobic oxidative carbonylation of methanol to dimethyl carbonate (DMC), J MOL CAT A, 175(1-2), 2001, pp. 51-63
The influence of the type and amount of added N-donor ligand, of the anion
and the oxidation state on the copper catalyzed aerobic oxidative carbonyla
tion of methanol to dimethyl carbonate (DMC) is systematically studied. A s
urprising increase in activity and selectivity compared to the plain copper
halides CuXn (X = Cl, Br, I; n = 1, 2) is found for catalyst complexes wit
h three or four N-methylimidazole (NMI) ligands at Cu+/2+, a ligand regime
reminiscent of the oxygen activating copper enzymes in nature. However, a l
arge excess of NMI inhibits the catalysis. The NMI complexes turned out to
be more active and selective as redox catalysts and less active in the comp
eting undesired hydrolytic cleavage of DMC into methanol and carbon dioxide
by the unavoidable byproduct water. Furthermore, corrosion of stainless st
eel autoclaves is efficiently inhibited in the presence of >2 eq. of NMI pe
r copper halide. (C) 2001 Elsevier Science B.V. All rights reserved.