Catalytic allylation of norbornadiene in the presence of Ni0 phosphite complexes resulting in 3-methylenetricyclo[4.2.1.02,5]non-7-ene was studied within the framework of the density functional theory using the PBE functional and the L11, L2, and L3 basis sets. According to calculations, the formation of the first C-C bond more likely proceeds involving the η3-allyl rather than η1-allyl ligand. The presence of one phosphite ligand favors the formation of the second C-C bond. Hydride transfer from the allyl moiety to the acetate ligand proceeds via an intermediate with agostic interaction. The highest energy on the reaction pathway (22.7 kcal mol−1) corresponds to the transition state of the formation of the first C-C bond.

中文翻译：

---

Ni0配合物存在下降冰片二烯与乙酸烯丙酯的相互作用：DFT模型

在密度泛函理论的框架内使用 PBE 泛函和 L11、L2 和 L3 研究了在 Ni0 亚磷酸酯配合物存在下催化烯丙基化降冰片二烯生成 3-亚甲基三环 [4.2.1.02,5]non-7-ene基组。根据计算，第一个 CC 键的形成更可能涉及 η3-烯丙基而不是 η1-烯丙基配体。一个亚磷酸酯配体的存在有利于形成第二个 CC 键。氢化物从烯丙基部分转移到乙酸盐配体通过具有激动相互作用的中间体进行。反应途径上的最高能量 (22.7 kcal mol-1) 对应于形成第一个 CC 键的过渡态。