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The influence of halogen anions and N‐ligands in CuXn/N‐ligands on the catalytic performance in oxidative carbonylation of methanol

“…The average leaching of Cu, which is the active constituent of the catalyst, was around 0.15%. Compared with other heterogenized catalysts used in the carbonylation of methanol to make DMC reported in the literature,15, 20–23 CuI/Phen–NH–PS is a reusable and efficient solid metal complex catalyst for the oxidative carbonylation of methanol with high catalytic activity, long lifetime, easy separation and low weight loss for each recycle.…”

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

“…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 particularly high activity and selectivity of the CuBr 2 -PyIL/SBA-15 catalyst in the present study may be attributed to the electronic modification of Cu(II) during the reaction of CuBr 2 with PyIL immobilized on SBA-15, which provides favorable environment for the production of DMC by the oxidative carbonylation of methanol.…”

“…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].…”

“…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]. Cao et al found CuCl immobilized on diamide modified mesoporous materials exhibited high activity and selectivity in the oxidative carbonylation of methanol [16].…”

Self‐Assembly from Two‐Dimensional Layered Networks to Tetranuclear Structures: Syntheses, Structures, and Properties of Four Copper–Thiacalix[4]arene Compounds

“…The formation of formate anions in 3 can be explained as the oxidation of methanol by the oxygen in air catalyzed by the Cu I -H 4 TC4A compound of 1. [13] A further study revealed that the deliberate addition of a small amount of water does result in a good yield of the target compounds, which might be attributed to the fact that the water molecules are not only involved in the crystal structures but are also helpful in the transformation of Cu I to Cu II and the formation of the formate anions. Possible reaction equations in the reassembly processes can be summarized as shown in Scheme 2.…”