Oxidative carbonylation of ethene catalyzed by Pd(II)–PPh₃ complexes in MeOH using benzoquinone as stoichiometric oxidant

Cavinato, Gianni; Facchetti, Sarah; Toniolo, Luigi

Oxidative carbonylation of ethene catalyzed by Pd(II)–PPh₃ complexes in MeOH using benzoquinone as stoichiometric oxidant

2012

Cavinato, Gianni | Facchetti, Sarah | Toniolo, Luigi

The complexes [Pd(COOMe)ₙX₂₋ₙ(PPh₃)₂] (n=0, 1, 2; X=TsO, OAc, ONO₂, Cl, Br), [Pd(SO₄)(PPh₃)₂], [PdCl₂(PPh₃)]₂ and PdX₂ (X=Cl, Br, I) catalyze the oxidative ethene carbonylation in MeOH using benzoquinone (BQ) as stoichiometric oxidant. The main products dimethyl succinate (DMS) and dimethyl oxalate (DMO) are formed together with minor amounts of methyl propanoate and dimethyl carbonate. The formation of DMS unambiguously proves that ethene inserts into a Pd–COOMe bond. The influence of the CO/ethene ratio at constant total pressure and of the BQ/Pd ratio on the product distribution has been studied. Model reactions of a Pd-hydride with BQ, of trans-[Pd(COOMe)(TsO)(PPh₃)₂] with ethene in the presence of BQ and of trans-[Pd(COOMe)₂(PPh₃)₂] with BQ have been studied by ³¹P{¹H} NMR. BQ consumes the Pd–hydride and directs the catalysis toward a Pd–COOMe initiator leading to DMS. In the catalysis to DMO, BQ is likely to favour the formation of a Pd–(COOMe)₂ species having the two carbomethoxy ligands in vicinal position such to favour the elimination of the product. The proposed catalytic cycles for the formation of the products are discussed.

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