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首页> 外文期刊>Organometallics >Mechanistic details of the nickel-mediated formation of acrylates from CO_2, ethylene and methyl iodide
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Mechanistic details of the nickel-mediated formation of acrylates from CO_2, ethylene and methyl iodide

机译：镍介导的CO_2，乙烯和甲基碘形成丙烯酸酯的机理的详细信息

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摘要

Methyl iodide induces the stoichiometric cleavage of nickelalactones, which are key intermediates in the nickel-mediated reaction of CO_2 and alkenes to acrylates. Herein, we propose a modified and extended mechanism for this reaction on the basis of theoretical and experimental investigations for the bidentate P ligand 1,2-bis(di-tert-butylphosphino)ethane (dtbpe). The calculated elementary steps agree well with experimental findings: reaction barriers are reasonable and explain the facile liberation of acrylate from a nickelalactone by methyl iodide. We were able to isolate reactive intermediates and to verify the existence of proposed reaction pathways. Additionally, we have identified unproductive pathways leading to byproducts (e.g., propionates and catalytically inactive organometallic species). Although those side reactions can be suppressed to a certain extent, the strong binding of acrylate to nickel prevents a catalytic reaction, at least for the chosen ligand.
机译：碘甲烷可诱导镍内酯的化学计量裂解，镍内酯是镍在二氧化碳和烯烃与丙烯酸之间的介导反应中的关键中间体。本文中，我们基于对双齿P配体1,2-双（二叔丁基膦基）乙烷（dtbpe）的理论和实验研究，提出了对该反应进行改进和扩展的机理。计算得出的基本步骤与实验结果非常吻合：反应障碍合理，可以解释甲基碘使丙烯酸酯从镍内酯中轻松释放出来。我们能够分离出反应性中间体，并验证提出的反应途径的存在。此外，我们发现了导致副产物（例如丙酸酯和催化惰性有机金属物质）的非生产性途径。尽管可以在一定程度上抑制这些副反应，但丙烯酸酯与镍的牢固结合至少在所选配体方面阻止了催化反应。

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