A kinetic and spectroscopic study on the copper catalyzed oxidative coupling polymerization of 2,6-dimethylphenol. X-ray structure of the catalyst precursor tetrakis(N-methylimidazole)bis(nitrato)copper(II)

The complex of copper(II) nitrate with N-methylimidazole (Nmiz) ligand has been studied as a catalyst for the oxidative coupling of 2,6-dimethylphenol by means of kinetic and spectroscopic measurements. The order of the reaction in copper is fractional and depends on the N/Cu ratio and the base/Cu ratio, indicating that there are at least two possible rate-determining steps, i.e. the formation of a dinuclear copper species and the phenol oxidation. EPR spectroscopy performed on frozen solutions with varying ligand to copper ratios shows that all Cu(II) is converted into the precursor complex at a ratio of 4 to 1, whereas in kinetic experiments, maximum activity and selectivity are reached only at a ratio of at least 30 to 1. Base is needed as a co-catalyst, and the maximum reaction rate is reached at a base to copper ratio of 1.8 to 1. The solid-state X-ray structure of the catalyst precursor complex has been determined to be [Cu(Nmiz)(4)(NO3)(2)], monoclinic, space group P2(1)/n, a=8.452(1)Angstrom, b=10.376(2)Angstrom, c=12.821(2)Angstrom, beta=94.88(2)degrees, Z=1, R=0.049 for 3525 reflections. This structure consists of an axially elongated octahedral CuN4O2 chromophore, which is in agreement with frozen-solution EPR spectra. Investigations under conditions where water and dioxygen were carefully excluded, have shown that for the phenol oxidation step the presence of dioxygen is not required. However, the reaction does require a trace of water (or hydroxide) to form the reactive intermediate. A modified reaction mechanism for the oxidative coupling is presented with special attention to the first steps of the reaction and the equilibrium species present in solution. The role of dioxygen appears to be only to reoxidize the formed Cu(I) species and to regenerate base.