Ligand effects in the copper catalyzed aerobic oxidative carbonylation of methanol to dimethyl carbonate (DMC)

Guanidine Metal Complexes for Bioinorganic Chemistry and Polymerisation Catalysis

“…During this reaction, the copper (I) complex reacts with O 2 in the presence of methanol under formation of a copper(II) methoxy species. The masked coordinated methoxy radicals are transferred to CO to give dimethyl carbonate and the initial copper(I) complex which allows to start the next cycle [61].…”

Oxidative carbonylation of methanol over copper ion-containing ionic liquids immobilized on SBA-15

“…In previous studies it has been found that anions have strong influence on the catalytic performance of copper compounds in the oxidative carbonylation of methanol [7]. The coordination environment of copper cations strongly affected the formation of reaction intermediates and Cu(II)/Cu(I) redox cycle in this reaction [7][8][9][10]15].…”

“…The synthesis of DMC by the oxidative carbonylation of methanol using a slurry CuCl catalyst in the liquid phase was firstly commercialized by Enichem in 1983. Since this process suffers from equipment corrosion, catalyst deactivation, and difficulties in product separation, a number of efficient homogeneous complex catalysts and copper salts catalysts immobilized on inorganic or organic solid materials have been extensively investigated in order to solve these problems [5][6][7][8][9][10][11][12][13][14][15][16][17][18]. For example, Raab and coworkers found that catalyst complexes with three or four N-methylimidazole ligands at Cu + / 2+ could increase both the conversion of methanol and the selectivity to DMC in comparison to the plain copper halides, whereas corrosion of the stainless steel reactors was efficiently inhibited [7].…”

“…Since this process suffers from equipment corrosion, catalyst deactivation, and difficulties in product separation, a number of efficient homogeneous complex catalysts and copper salts catalysts immobilized on inorganic or organic solid materials have been extensively investigated in order to solve these problems [5][6][7][8][9][10][11][12][13][14][15][16][17][18]. For example, Raab and coworkers found that catalyst complexes with three or four N-methylimidazole ligands at Cu + / 2+ could increase both the conversion of methanol and the selectivity to DMC in comparison to the plain copper halides, whereas corrosion of the stainless steel reactors was efficiently inhibited [7]. Sato et al investigated the performance of heterogenized CuCl 2 catalysts supported on polymers containing N-donor ligand aromatics and found that those catalysts could be easily recovered, and the initial catalytic activity was maintained after three recycle [12][13][14][15].…”

Catalytic Properties of Cu Complexes in Oxidative Carbonylation of Methanol

“…Considering that the solubility of CuCl in methanol is very low, CuCl 2 is chosen as the copper source. Raab et al has found that NMI could improve the activity of CuCl 2 greatly and reduce the corrosion of the autoclave [5].…”