Versatile PdTe/C catalyst for liquid-phase oxidations of 1,3-butadiene

• PdTe/C catalyst can participate competing radical chain and heterolytic route in liquid-phase oxidation of 1,3-butadiene.
• Specific location of tellurium on the surface of palladium particles in the catalyst.
• High selectivity to 1,4-butenediol derivatives in DMA (61%) and MeOH (84%).

A commercial Pd catalyst based on Sibunit carbon support was treated with H6TeO6 in a reducing media to obtain a Te coating on the surface of Pd particles. The PdTe/C catalyst prepared in this way showed the ability to control the radical chain oxidation of 1,3-butadiene by promoting the selective formation of 2-butene-1,4-diol, 4-hydroxybut-2-enal and furan in DMA (total selectivity of 61% and yield of 7%). At the same time, the catalyst induced oxidation of 1,3-butadiene by a non-radical heterolytic mechanism involving the formation of two groups of primary products: (1) сrotonaldehyde and methyl vinyl ketone and (2) the products of oxygenation at the 1,4-positions. The compounds of the second group including 1,4-dimethoxy-2-butene and maleic acid dimethyl ester were formed on PdTe centers in MeOH. Increasing the Te concentration in the PdTe/C catalyst forced the conversion of 1,3-butadiene toward 1,4-oxygenation and simultaneously decreased the intensity of secondary oxidation, resulting in the selective formation of derivatives of the 1,4-oxygenation—1,4-dimethoxy-2-butene and allenic alcohol methyl ether (total selectivity of 84% and yield of 48%).

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