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The objectives of this work were to address the fundamental characteristics of ansa-zirconocene catalyzed E/diene copolymerization and E/diene/1-hexene and E/diene/propylene terpolymerizations, and the quantitative relationship between diene structure and polymer chain propagation rate constant in term of quantifiable catalytic active sites. One of the most important but unknown factors in olefins ansa-zirconocene complexes is the distribution of the catalyst between sites actively participating in polymer chain formation and dormant sites. A set of ethylene/dienes copolymerizations, and ethylene/dienes/1-hexene and ethylene/dienes/1-hexene terpolymerizations catalyzed with