Several Au(III)/Schiff-base complexes were studied and proven to be effective catalysts for oxidative carbonylation of methanol to generate dimethyl carbonate (DMC). Effects of Schiff-base ligands, promoters, and promoter mole ratio to Au(III)/Schiff-base complexes on catalytic activity were studied. When the reaction was carried out at a methanol/Au(III) molar ratio of 5060:1, an [AuCl 2(phen)]Cl/KI (phen = 1,10-phenanthroline) ratio of 1:4, a CO/O 2 pressure of 2:1, and a temperature of 120 °C for 3 h, the conversion, selectivity, and TOF value of the model reaction were 10.8%, 98%, and 138.9 h −1, respectively. The catalyst was characterized by FTIR, UV–vis, 1H NMR, and cyclic voltammetry. The oxidation state of gold during the reaction and the role of KI were discussed using data on electrochemical experiments and ESI-MS. [AuI 2(phen)] + was considered an intermediate in the reaction. A plausible Au(III)/Au(I) catalytic cycle mechanism was proposed.
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