摘要
This paper reports the kinetics of the oxidation of 2,6-dimethylphenol (DMP) to get 3,3’,5,5’-tetra- methyl-4,4’-diphenoquinone (DPQ) using novel oxidative coupling complexes [(Pip)<sub>4n</sub>Cu<sub>4</sub>X<sub>4</sub>-(CO<sub>3</sub>)<sub>2</sub>] (n = 1 or 2, X = Cl or Br, Pip = piperidine). The new prepared tetranuclear complexes were characterized using cryoscopic measurements, electronic spectra, FTIR, EPR and cyclic voltammetry techniques. These complexes are catalytically active. The proposed mechanism of the catalytic oxidative coupling can be illustrated as a pre-equilibrium, K, between the catalyst and DMP to form a complex intermediate which is converted to activated complex through the rate determining step, k<sub>2</sub>, to form the final product. The inverse of the observed rate constants k<sub>obsd</sub> versus 1/[DMP]<sup>2</sup> gives a straight line with intercept. From the slope and the intercept, both K and k<sub>2</sub> are obtained. At different temperatures, thermodynamic and kinetic parameters are evaluated. It is worth to mention that, the dependence of k<sub>obsd</sub> on [DMP]<sup>2</sup> indicates that the coordination number for every copper center in both n = 1 or 2 in [(Pip)<sub>4n</sub>Cu<sub>4</sub>X4(CO<sub>3</sub>)<sub>2</sub>] is equal to six. Therefore, carbonato bridging centers in n = 1 acts as a tridentate ligand, while for n = 2 acts as a bidentate ligand.
This paper reports the kinetics of the oxidation of 2,6-dimethylphenol (DMP) to get 3,3’,5,5’-tetra- methyl-4,4’-diphenoquinone (DPQ) using novel oxidative coupling complexes [(Pip)<sub>4n</sub>Cu<sub>4</sub>X<sub>4</sub>-(CO<sub>3</sub>)<sub>2</sub>] (n = 1 or 2, X = Cl or Br, Pip = piperidine). The new prepared tetranuclear complexes were characterized using cryoscopic measurements, electronic spectra, FTIR, EPR and cyclic voltammetry techniques. These complexes are catalytically active. The proposed mechanism of the catalytic oxidative coupling can be illustrated as a pre-equilibrium, K, between the catalyst and DMP to form a complex intermediate which is converted to activated complex through the rate determining step, k<sub>2</sub>, to form the final product. The inverse of the observed rate constants k<sub>obsd</sub> versus 1/[DMP]<sup>2</sup> gives a straight line with intercept. From the slope and the intercept, both K and k<sub>2</sub> are obtained. At different temperatures, thermodynamic and kinetic parameters are evaluated. It is worth to mention that, the dependence of k<sub>obsd</sub> on [DMP]<sup>2</sup> indicates that the coordination number for every copper center in both n = 1 or 2 in [(Pip)<sub>4n</sub>Cu<sub>4</sub>X4(CO<sub>3</sub>)<sub>2</sub>] is equal to six. Therefore, carbonato bridging centers in n = 1 acts as a tridentate ligand, while for n = 2 acts as a bidentate ligand.
