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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Oxidation of Pd(ii) with disilane in a palladium-catalyzed disilylation of aryl halides: a theoretical view
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Oxidation of Pd(ii) with disilane in a palladium-catalyzed disilylation of aryl halides: a theoretical view

机译：用钯催化芳基亚卤化物的苯胺甲硅烷氧化硅烷氧化Pd（II）：理论观点

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Density functional theory (DFT) calculation has been used to reveal the mechanism of the Pd-catalyzed disilylation reaction of aryl halides. The DFT calculations indicate that the reaction starts with the oxidative addition of the C-I bond to the Pd(0) catalyst. Concerted metalation-deprotonation (CMD) can then generate a five-membered palladacycle. Insertion of Pd(ii) into the Si-Si bond in disilane followed by two sequential steps of reductive eliminations yields the disilylation product and regenerates the Pd(0) catalyst. According to the NPA charge analysis along the reaction coordinates, the formal oxidative addition of the Si-Si bond to palladium could be considered as the insertion of palladium into the Si-Si bond. However, the conventional oxidative addition of the C-I bond to palladium is exactly an oxidation process with the electron transfer from the palladium atom to the C-I bond. Therefore, electron rich Pd(0) is beneficial for the oxidation process, and Pd(ii) prone to acquire electrons is beneficial for the insertion process.
机译：利用密度泛函理论（DFT）计算揭示了钯催化的卤代芳基二硅烷基化反应的机理。DFT计算表明，该反应始于C-I键对Pd（0）催化剂的氧化加成。协同金属化脱质子（CMD）可以生成五元帕拉达环。将Pd（ii）插入二硅烷中的Si-Si键中，然后进行两个连续的还原消除步骤，得到二硅烷基化产物并再生Pd（0）催化剂。根据沿反应坐标的NPA电荷分析，Si-Si键与钯的正式氧化加成可视为钯插入Si-Si键。然而，C-I键与钯的传统氧化加成正是一个氧化过程，电子从钯原子转移到C-I键。因此，富含电子的Pd（0）有利于氧化过程，而易于获得电子的Pd（ii）有利于插入过程。

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