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首页> 外文期刊>Chemistry: A European journal >Computational Study of the Palladium-Catalyzed Carbonylative Synthesis of Aromatic Acid Chlorides: The Synergistic Effect of PtBu3 and CO on Reductive Elimination
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Computational Study of the Palladium-Catalyzed Carbonylative Synthesis of Aromatic Acid Chlorides: The Synergistic Effect of PtBu3 and CO on Reductive Elimination

机译：钯催化芳族酰氯羰基化合成的计算研究：PtBu3和CO协同作用的还原消除

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摘要

We describe herein computational studies on the unusual ability of Pd(PtBu3)(2) to catalyze formation of highly reactive acid chlorides from aryl halides and carbon monoxide. These show a synergistic role of carbon monoxide in concert with the large cone angle PtBu3 that dramatically lowers the barrier to reductive elimination. The tertiary structure of the phosphine is found to be critical in allowing CO association and the generation of a high energy, four coordinate (CO)(PR3)Pd(COAr)Cl intermediate. The stability of this complex, and the barrier to elimination, is highly dependent upon phosphine structure, with the tertiary steric bulk of PtBu3 favoring product formation over other ligands. These data suggest that even difficult reductive eliminations can be rapid with CO association and ligand manipulation. This study also represents the first detailed exploration of all the steps involved in palladium-catalyzed carbonylation reactions with simple phosphine ligands, including the key rate-determining steps and palladium(0) catalyst resting state in carbonylations.
机译：我们在此描述有关Pd（PtBu3）（2）催化由芳基卤化物和一氧化碳形成高反应性酰氯的异常能力的计算研究。这些表明一氧化碳与大锥角PtBu3协同作用，大大降低了还原消除的障碍。发现膦的三级结构对于允许CO缔合和产生高能的四配位（CO）（PR3）Pd（COAr）Cl中间体至关重要。该配合物的稳定性以及消除的障碍高度依赖于膦的结构，PtBu3的叔空间体积比其他配体更有利于产物形成。这些数据表明，即使很困难的还原消除也可以通过CO缔合和配体操纵而迅速完成。这项研究还代表了使用简单的膦配体进行的钯催化羰基化反应涉及的所有步骤的首次详细探索，包括关键的速率决定步骤和羰基化中钯（0）催化剂的静止状态。

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