{"title":"金属钯是在烯烃的瓦克氧化中形成的吗?","authors":"Milan Hronec, Zuzana Cvengrošová, Štefan Holotík","doi":"10.1016/0304-5102(94)00043-3","DOIUrl":null,"url":null,"abstract":"<div><p>The oxidation of cyclohexene with molecular oxygen catalyzed by solid Pd/C or Pd<sup>II</sup> 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 Pd<sup>0</sup> centres intermediately formed after stoichiometric oxidation of cyclohexene by Pd<sup>II</sup> 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.</p></div>","PeriodicalId":16567,"journal":{"name":"分子催化","volume":"91 3","pages":"Pages 343-352"},"PeriodicalIF":0.0000,"publicationDate":"1994-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/0304-5102(94)00043-3","citationCount":"6","resultStr":"{\"title\":\"Is metallic palladium formed in Wacker oxidation of alkenes?\",\"authors\":\"Milan Hronec, Zuzana Cvengrošová, Štefan Holotík\",\"doi\":\"10.1016/0304-5102(94)00043-3\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>The oxidation of cyclohexene with molecular oxygen catalyzed by solid Pd/C or Pd<sup>II</sup> 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 Pd<sup>0</sup> centres intermediately formed after stoichiometric oxidation of cyclohexene by Pd<sup>II</sup> 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.</p></div>\",\"PeriodicalId\":16567,\"journal\":{\"name\":\"分子催化\",\"volume\":\"91 3\",\"pages\":\"Pages 343-352\"},\"PeriodicalIF\":0.0000,\"publicationDate\":\"1994-07-29\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://sci-hub-pdf.com/10.1016/0304-5102(94)00043-3\",\"citationCount\":\"6\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"分子催化\",\"FirstCategoryId\":\"1089\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/0304510294000433\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q4\",\"JCRName\":\"Chemical Engineering\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"分子催化","FirstCategoryId":"1089","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/0304510294000433","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"Chemical Engineering","Score":null,"Total":0}
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.