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High Resolution Image Download MS PowerPoint Slide A mechanistic study investigating reactivity differences in metallocene-mediated cationic ring-opening homo- and copolymerization (CROP) of 2- R -oxazolines (R = Me, Ph) and ε-caprolactone (CL) is reported. Using density functional theory at the M06-2X level, we examined sequential monomer addition pathways, focusing on the C–O bond insertion mechanisms. Gibbs activation energies reveal a clear reactivity trend: CLcoMeOX 0.6) between Gibbs activation energies and electronic and structural parameters, including Zr–B distances, atomic charges, and electron density distributions. These insights provide specific guidelines for optimizing metallocene-mediated CROP and offer a theoretical foundation for designing well-defined block copolymers with controlled architectures.
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