Olefin and diene transformations, catalyzed by organoaluminum-activated metal complexes, are widely used in synthetic organic chemistry and form the basis of major petrochemical processes. However, the role of M−(μ-Cl)−Al bonding, being proven for certain >C=C< functionalization reactions, remains unclear and debated for essentially more important industrial processes such as oligomerization and polymerization of α-olefins and conjugated dienes. Numerous publications indirectly point at the significance of M−(μ-Cl)−Al bonding in Ziegler−Natta and related transformations, but only a few studies contain experimental or at least theoretical evidence of the involvement of M−(μ-Cl)−Al species into catalytic cycles. In the present review, we have compiled data on the formation of M−(μ-Cl)−Al complexes (M = Ti, Zr, V, Cr, Ni), their molecular structure, and reactivity towards olefins and dienes. The possible role of similar complexes in the functionalization, oligomerization and polymerization of α-olefins and dienes is discussed in the present review through the prism of the further development of Ziegler−Natta processes and beyond.
Keywords: DFT; Ziegler–Natta catalysts; carboalumination; dienes; heterobimetallic complexes; hydroalumination; metallocenes; methylenealkanes; olefins; oligomerization; polymerization; polyolefins; single-site catalysts.