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Abstract：
In a combined experimental and computational study, the isomerization activity of the dinuclear palladium(I) complex [PdI (μ-Br)(Pt Bu3 )]2 towards allyl arenes, esters, amides, ethers, and alcohols has been investigated. The calculated energy profiles for catalyst activation for two alternative dinuclear and mononuclear catalytic cycles, and for catalyst deactivation are in good agreement with the experimental results. Comparison of experimentally observed E/Z ratios at incomplete conversion with calculated kinetic selectivities revealed that a substantial amount of product must form via the dinuclear pathway, in which the isomerization is promoted cooperatively by two palladium centers. The dissociation barrier towards mononuclear Pd species is relatively high, and once the catalyst enters the energetically more favorable mononuclear pathway, only a low barrier has to be overcome towards irreversible deactivation.
摘要：
在一项实验和计算相结合的研究中，双核钯（I）配合物[PdI（μ-Br）（PtBu3）]2对烯丙基芳烃的异构化活性，酯类,酰胺,醚,和酒精已经被调查。计算出的两个替代双核和单核催化循环的催化剂活化能量曲线，催化剂失活与实验结果吻合较好。在不完全转化下实验观察到的E/Z比与计算的动力学选择性的比较表明，必须通过双核途径形成大量的产物，其中异构化由两个钯中心协同促进。单核Pd物种的解离屏障相对较高，一旦催化剂进入能量更有利的单核途径，只有一个低障碍必须克服不可逆转的失活。
