Preliminary Communication
New aspects of the synthesis of dimethyl carbonate via carbonylation of methyl alcohol promoted by methoxycarbonyl complexes of palladium(II)

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Abstract

[PdCl2(PPh3)2] suspended in MeOH reacts with carbon monoxide (40–80 atm, 50°C), in the presence of a base such as NEt3 to give the methoxycarbonyl complex trans-[PdCl(COOMe)(PPh3)2]. When the carbonylation reaction is carried out at 90–100°C reduction to Pd0 carbonyl-phosphine complexes occurs, with formation of dimethyl carbonate, selectively and in an almost quantitative yield. The above complexes are less reactive than the acetato-analogues, which give dimethyl oxalate as the main organic carbonylation product even at 50°C.

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