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Palladium-mediated radical homocoupling reactions: a surface catalytic insight

机译：Palladium-mediated激进homocoupling反应:一个表面催化的洞察力

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摘要

In this contribution, we report a palladium nanoparticle-promoted reductive homocoupling of haloarenes that proceeds efficiently to produce corresponding bis-aryls in moderate to excellent yields using relatively low catalyst loading (1 mol%), and exhibits broad functional group tolerance. This work sheds light on how the surface state of Pd(0) nanoparticles plays a crucial role in the reactivity of catalytic systems. Notably, the appropriate choice of palladium salts for the preparation of the preformed nanocatalysts was a key parameter having a major impact on the catalytic activity; thus, the effect of halide anions on the reactivity of the as-prepared palladium nanoparticles could be assessed, with iodide anions being capable of inhibiting the corresponding homocoupling reaction. The homocoupling reaction mechanism has been further studied by means of radical trap and electron paramagnetic resonance (EPR) experiments, revealing that the reaction proceeds via radical intermediates. Taking into account these data, a plausible reaction mechanism based on single-electron transfer processes on the palladium nanoparticle surface is discussed.
机译：在这个贡献,我们报告一个钯nanoparticle-promoted还原homocoupling的haloarenes,高效生产相应bis-aryls中度到优秀使用相对较低的催化剂装入收益率(1摩尔%),表现出广泛的官能团宽容。Pd(0)纳米粒子的表面状态起着催化反应的关键作用系统。钯盐的制备预制nanocatalysts是一个关键参数有一个主要对催化活性的影响;因此,卤离子的影响反应性和钯纳米颗粒可以评估,与碘化负离子被抑制的能力相应homocoupling反应。homocoupling进一步反应机制研究了通过激进的陷阱和电子顺磁共振(EPR)的实验中,显示通过激进的反应所得中间体。基于合理的反应机制单电子转移过程讨论了钯纳米颗粒表面。

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