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Abstract
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Metallocene-based catalysis enables highly efficient and precise polymerisation of olefins, diolefins, and styrenic monomers, offering exceptional control over polymer microstructure and architecture. Despite substantial progress, particularly with ansa-metallocenes, key questions remain regarding how ligand environments, bridge architectures, and metal-centre electronics collectively govern polymer properties such as molecular weight, dispersity (Ð), and thermal stability. In this review, we have provided a significant advance toward understanding active-site formation and mechanistic insights into chain-growth behaviour and molecular-weight distribution with recent literature. Moreover, variations in catalyst performance under different reaction conditions highlight the need for standardised evaluation protocols. This review also examines how catalyst structure and critical operational parameters, temperature, pressure, monomer-to-catalyst ratio, solvent, and reaction time, shape polymerisation outcomes. Special emphasis is placed on kinetic studies, particularly quench-based active-site quantification, an effective yet underused tool for probing catalyst dynamics. The discussion also underscores the often-overlooked role of chain-transfer processes in determining polymer properties and processing behavior. Together, these perspectives outline current limitations in metallocene catalyst design and point to improved strategies to achieve greater precision and efficiency in polyolefin synthesis.
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