This computational study explores the copper (I) chloride catalyzed synthesis of (E)-1-(2,2-dichloro-1-phenylvinyl)-2-phenyldiazene (2Cl-VD) from readily available hydrazone derivative and carbon tetrachloride (CCl₄). 2Cl-VD has been extensively utilized to synthesize variety of heterocyclic organic compounds in mild conditions. The present computational investigations primarily focus on understanding the role of copper (I) and N¹,N¹,N²,N²-tetramethylethane-1,2-diamine (TMEDA) in this reaction, TMEDA often being considered a proton scavenger by experimentalists. Considering TMEDA as a ligand significantly alters the energy barrier. In fact, it is only 8.3 kcal/mol higher compared to the ligand-free (LF) route for the removal of a chlorine atom to form the radical ·CCl₃ but the following steps are almost barrierless. This intermediate then participates in attacking the electrophilic carbon in the hydrazone. Crucially, the study reveals that the overall potential energy surface is thermodynamically favorable, and the theoretical turnover frequency (TOF) value is higher in the case of Cu(I)-TMEDA complex catalyzed pathway.

中文翻译：

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铜(I)催化腙转化为二卤代乙烯基二氮烯衍生物的计算探索


这项计算研究探讨了氯化亚铜 (I) 催化从现成的腙衍生物和四氯化碳 (CCl < b0>）。 2Cl-VD已被广泛用于在温和条件下合成各种杂环有机化合物。目前的计算研究主要集中于了解铜 (I) 和 N ¹ 、N ¹ 、N ² 、N ² -四甲基乙烷-1,2-二胺 (TMEDA) 在该反应中，TMEDA 通常被实验学家认为是质子清除剂。将 TMEDA 视为配体会显着改变能垒。事实上，与去除氯原子形成自由基·CCl ₃ 的无配体 (LF) 路线相比，仅高 8.3 kcal/mol，但后续步骤几乎无障碍。然后该中间体参与攻击腙中的亲电子碳。至关重要的是，研究表明，在 Cu(I)-TMEDA 复合催化途径的情况下，整体势能表面在热力学上是有利的，并且理论转换频率 (TOF) 值更高。