Abstract

We focus on the synthesis, characterization, and theoretical analysis of a novel zirconocene complex derived from substituted 2,7-diethyl-1,8-dihydro-as-indacene (as-Ic'H2).This complex [(Cp*ZrCl2)2-as-Ic´], was synthesized from the dilithiated salt of as-indacene [as-Ic´][Li]2 with two equivalents of [(Cp*ZrCl3)]. Comprehensive characterization was performed using 1H and 13C NMR spectroscopy, elemental analysis, and X-ray diffraction. Density Functional Theory (DFT) calculations revealed that the dicationic pathway for ethylene polymerization exhibits enhanced thermodynamic stability and favorable orbital interactions, offering a more efficient initiation process than the cationic pathway. However, higher activation barriers were identified in the dicationic pathway, suggesting that targeted steric modifications could further optimize catalytic performance. These findings provide strategic insights for designing more effective bimetallic zirconocene catalysts. © 2025 Elsevier B.V.