The most challenging step in the production of acrylates from ethylene and CO2 mediated by transition-metal complexes is the release of the acrylate from the metallalactone intermediate formed by coupling of ethylene and CO2. Recently, methyl acrylate formation was achieved from nickelalactones by using methyl iodide (MeI) as the electrophile, and the yield was tuned with different amine and phosphine ligands. Modeling organometallic catalysts with such large ligands accurately is a challenge for computational chemistry. A hybrid approach has been designed here by coupling the double hybrid XYG3 and the hybrid B3LYP exchange correlation functionals, using the extended ONIOM scheme. This approach was then applied to explore the role of the MeI electrophile for the formation of methyl acrylate from the initial nickelalactone complex and to rationalize the effect of the ligands on the yield of methyl acrylate. We show that the choice of ligand has little effect on the main productive pathway. However, it has a significant influence on side reactions, which compete with the productive pathway and are detrimental to methyl acrylate formation. Finally, the need for a very large overstoichiometry of MeI for a good yield of methyl acrylate is explained by the lower polarity of MeI, which avoids the stabilization of nonproductive intermediates. The nature of the limiting intermediates has been validated by comparing calculated and experimental vibrational spectra.