New density functional theory (DFT) computations are reported concerning the mechanism of the Suzuki-Miyaura cross-coupling reaction of aryl halides and aryl boronic acids catalyzed by palladium phosphine complexes. The calculations are aimed at refining the understanding of the overall catalytic mechanism using state of the art theoretical approaches (including, for the first time, an attempt to describe the Gibbs energy of the reactant base in a realistic way). New experimental results (Thomas and Denmark, Science, 2016, 352, 329-332) concerning pre-transmetallation intermediates with a Pd-O-B linkage provide an invaluable benchmark to test the accuracy of the calculations. The calculations show that bottlenecks to catalysis associated with oxidative addition, X-to-O substitution at Pd, and transmetallation can lie close in energy.

中文翻译：

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Suzuki-Miyaura耦合重新研究：一项综合计算研究。

报道了有关钯膦配合物催化的芳基卤化物和芳基硼​​酸的Suzuki-Miyaura交叉偶联反应机理的新密度泛函理论（DFT）计算。该计算旨在利用最先进的理论方法（包括首次尝试以现实的方式描述反应物碱的吉布斯能量）来加深对整体催化机理的理解。关于具有Pd-OB键的重金属化前中间体的新实验结果（Thomas and Denmark，Science，2016，352，329-332）提供了宝贵的基准来测试计算的准确性。计算表明，与氧化加成，Pd上X到O的取代以及重金属化相关的催化瓶颈可能与能量紧密相关。