Carbonate formation by the reaction of cupric methoxide and carbon monoxide

Organic Carbonates

“…The formation of dialkyl carbonates from the reaction of alcohols and carbon monoxide has been reported to be promoted by transition metal compounds (in particular palladium, mercury, and copper) and post-transition-metal compounds . In the case of palladium and mercury, however, the reaction does not seem to be selective and involves reduction to the metal, which can not be reoxidized directly.…”

Theoretical Analysis of Oxidative Carbonylation of Methanol: Saegusa’s Scheme of Dimethylcarbonate Synthesis over Binuclear Cationic Oxo-Clusters in CuNaX Zeolite

“…In ref 7, authors referenced the experimental value 14.80 kcal/mol for CuY, while the lower apparent activation energy near 11.70 kcal/mol for DMC production within a close interval of 380− 430 K has been measured on the ZSM-5. 4 Together with two mechanisms for oxidative carbonylation of methanol via methoxy species 7,8,16 and carbomethoxy species, 1,3,9,11,12,17 two other channels were proposed via carbonates 6,19 and >Cu(OCH 3 ) 2 Cu< species (the last is named below as Saegusa's scheme). 2,13 The first three of them were analyzed theoretically including the route through carbonates.…”

“…Two principal mechanisms have been proposed for the carbonylation. The first one is via the formation of DMC via Cu + (CH 3 OCO) carbomethoxides and Cu + (OCH 3 ) methoxides ,,− where Z denotes a zeolite framework. The second route assumes the formation of monomethylcarbonates (MMC) and methoxides: ,,− …”

“…Together with two mechanisms for oxidative carbonylation of methanol via methoxy species ,, and carbomethoxy species, ,,,,, two other channels were proposed via carbonates , and >Cu­(OCH 3 ) 2 Cu< species (the last is named below as Saegusa’s scheme). , The first three of them were analyzed theoretically including the route through carbonates . The methoxy intermediate route at one Cu + center was first theoretically studied in ref (without theoretical estimation of the activation energy) and then reconsidered in ref .…”