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Palladium (II)‐catalyzed homogeneous alcohol oxidations: Disclosing the crucial contribution of palladium nanoparticles in catalysis
Applied Organometallic Chemistry ( IF 3.7 ) Pub Date : 2020-11-20 , DOI: 10.1002/aoc.6093 Miao Zeng 1 , Chenlin Lou 1 , Jing‐Wen Xue 1 , Hongwu Jiang 1 , Kaiwen Li 1 , Zhuqi Chen 1 , Shitao Fu 1 , Guochuan Yin 1
Applied Organometallic Chemistry ( IF 3.7 ) Pub Date : 2020-11-20 , DOI: 10.1002/aoc.6093 Miao Zeng 1 , Chenlin Lou 1 , Jing‐Wen Xue 1 , Hongwu Jiang 1 , Kaiwen Li 1 , Zhuqi Chen 1 , Shitao Fu 1 , Guochuan Yin 1
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Versatile redox catalysts play the significant roles in alcohol oxidations, in which the mechanisms for homogeneous and heterogeneous alcohol oxidations are generally different. This work introduced a Lewis acid (LA) promoted homogeneous alcohol oxidation with Pd (OAc)2 catalyst by using oxygen balloon as the oxidant source. It was found that adding Lewis acid such as Sc (OTf)3 significantly accelerated Pd (II)‐catalyzed alcohol oxidations; notably, the time courses of oxidations monitored by GC and 1H NMR disclosed that there existed two processes including the initial sluggish oxidation followed by a rapid oxidation. The promotional effect of Lewis acid was attributed to the formation of heterobimetallic Pd (II)/LA species, which improved the oxidizing power of the palladium (II) species, thus accelerating alcohol oxidation in the induction period. Correlating the sizes of in situ generated palladium nanoparticles with the time course of alcohol oxidation further disclosed that the loosely, spherically large nanoparticles, which were composed of many tiny nanoparticles having the size less than 10 nm, were responsible for the rapid oxidation, whereas those highly dispersed, tiny nanoparticles having the size less than 10 nm were not responsible for the rapid oxidation.
中文翻译：
钯（II）催化的均相醇氧化：揭示钯纳米颗粒在催化中的关键作用
多功能氧化还原催化剂在醇氧化中起重要作用，其中均相和异相醇氧化的机理通常不同。这项工作介绍了路易斯酸（LA）通过使用氧气气球作为氧化剂源，以Pd（OAc）2催化剂促进均相醇氧化。研究发现，添加路易斯酸（例如Sc（OTf）3）可显着加速Pd（II）催化的醇氧化。值得注意的是，GC和11 H NMR表明存在两个过程，包括最初的缓慢氧化和随后的快速氧化。路易斯酸的促进作用归因于杂双金属Pd（II）/ LA物种的形成，这改善了钯（II）物种的氧化能力，从而加速了诱导期的醇氧化。将原位生成的钯纳米粒子的大小与酒精氧化的时间进程进行关联，进一步揭示了由许多小于10 nm的微小纳米粒子组成的松散球形球形纳米粒子是快速氧化的原因，而那些高度分散，尺寸小于10 nm的微小纳米颗粒与快速氧化无关。
更新日期：2021-01-27
中文翻译：
钯（II）催化的均相醇氧化：揭示钯纳米颗粒在催化中的关键作用
多功能氧化还原催化剂在醇氧化中起重要作用，其中均相和异相醇氧化的机理通常不同。这项工作介绍了路易斯酸（LA）通过使用氧气气球作为氧化剂源，以Pd（OAc）2催化剂促进均相醇氧化。研究发现，添加路易斯酸（例如Sc（OTf）3）可显着加速Pd（II）催化的醇氧化。值得注意的是，GC和11 H NMR表明存在两个过程，包括最初的缓慢氧化和随后的快速氧化。路易斯酸的促进作用归因于杂双金属Pd（II）/ LA物种的形成，这改善了钯（II）物种的氧化能力，从而加速了诱导期的醇氧化。将原位生成的钯纳米粒子的大小与酒精氧化的时间进程进行关联，进一步揭示了由许多小于10 nm的微小纳米粒子组成的松散球形球形纳米粒子是快速氧化的原因，而那些高度分散，尺寸小于10 nm的微小纳米颗粒与快速氧化无关。
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