金属钯是在烯烃的瓦克氧化中形成的吗?

Q4 Chemical Engineering
Milan Hronec, Zuzana Cvengrošová, Štefan Holotík
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引用次数: 6

摘要

在固体Pd/C或醋酸PdII -对苯二酚-酞菁铁催化下,环己烯与分子氧氧化得到环己烷、苯和氧合产物。氧气压力和溶剂的使用对产物的分布有显著影响,在2atm以上的压力下,不形成环己烷。在无氧的Pd/C催化剂上,歧化反应只发生在环己烷和苯上(比例接近2:1)。在相同条件下,2-环己醇歧化成环己醇和苯酚,部分重排成环己酮。瓦克条件下环己烯歧化反应的解释是,环己烯被PdII化学氧化后中间形成的Pd0中心没有完全再氧化,但根据反应条件,它们可以部分聚集,然后,类似于金属表面,将环己烯脱氢成苯。形成的氢迁移到钯表面,使环己烯氢化或在足够的氧压下被氧化成水。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Is metallic palladium formed in Wacker oxidation of alkenes?

The oxidation of cyclohexene with molecular oxygen catalyzed by solid Pd/C or PdII acetate—hydroquinone—iron phthalocyanine gives cyclohexane, benzene and oxygenated products. Oxygen pressure and solvent used influence significantly the distribution of the products and at the pressure above 2 atm no cyclohexane is formed. Over Pd/C catalyst in the absence of oxygen, disproportionation to cyclohexane and benzene (the ratio is nearly 2:1) proceeds exclusively. Under comparable conditions 2-cyclohexenol is disproportionated to cyclohexanol and phenol and some of it rearranges to cyclohexanone. The explanation for the disproportionation of cyclohexene under the Wacker conditions is that Pd0 centres intermediately formed after stoichiometric oxidation of cyclohexene by PdII are not completely reoxidized, but depending on the reaction conditions, they can partly aggregate and then, similarly to metallic surfaces, dehydrogenate cyclohexene to benzene. The hydrogen species formed migrate on the palladium surface and hydrogenate cyclohexene or at sufficient oxygen pressure they are oxidized to water.

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来源期刊
分子催化
分子催化 Chemical Engineering-Catalysis
CiteScore
1.50
自引率
0.00%
发文量
2959
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