Modulating selectivity in polymerization catalysis through noncovalent interactions: insights from experiments and DFT studies

This review explores the role of noncovalent interactions (NCIs) in governing selectivity in polymerization catalysis, integrating evidence from experimental studies and density functional theory (DFT) calculations. The discussion covers a wide range of catalytic systems, from α-olefin polymerizations mediated by transition-metal complexes to the ring-opening (co)polymerization of biodegradable polymers promoted by organometallic and organocatalytic species. Analysis of NCIs through DFT modeling highlights their crucial influence on catalyst performance, emphasizing how interactions among the catalyst, monomer, and growing polymer chain may affect polymerization selectivity. Particular attention is given to representative cases where NCIs, such as hydrogen bonding and C–H⋯F interactions, play a crucial mechanistic role. Finally, the review extends the discussion to the contribution of NCIs in polymer stereocomplexation, underscoring their impact not only on polymerization mechanisms but also on the resulting material properties.