Interaction of norbornadiene with allyl acetate in the presence of Ni0 complexes: a DFT modeling

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.