Mechanism and Stereoselectivity Control of Terminal Alkyne Dimerization Activated by a Zr/Co Heterobimetallic Complex: A DFT Study

Heterobimetallic complexes have recently garnered considerable attention in organic synthesis owing to their high activity and selectivity, which surpass those of monometallic complexes. In this study, the detailed mechanisms of terminal alkyne dimerization activated by the heterobimetallic Zr/Co complex, as well as the different stereoselectivities of Me3SiCCH and PhCCH dimerization, were investigated and elucidated by using density functional theory calculations. After excluding the three-molecule reaction and outer-sphere mechanisms, the inner-sphere mechanism was determined as the most optimal process. The inner-sphere mechanism involves four processes: THF dissociation and coordination of the first alkyne; ligand migration and C–H activation; N2 dissociation and insertion of the second alkyne; and reductive elimination. The stereoselectivity between the E-/Z- and gem-isomers is determined by the C–C coupling mode of the two alkynes and that of the E- and Z-isomers is determined by the sequence of the C–C coupling and hydrogen migration in the reductive elimination process. Me3SiCCH dimerization yields only an E-isomer owing to the large differences in the distortion and interaction energies, whereas PhCCH dimerization produces an E-, Z-, and gem-isomers owing to the reduced interaction energy differences.