A series of cobalt complexes bearing (8-(arylimino)-5,6,7-trihydroquinolin-2-yl)methyl acetate ligand framework were prepared using a one-pot synthesis method. These complexes were then extensively investigated for their catalytic performance in isoprene polymerization. In addition to the complexes being characterized via FT-IR spectrum and elemental analysis, the molecular structure of Co1 and Co5 was determined via X-ray diffraction analysis. The analysis revealed a chloride-bridged centrosymmetric binuclear species in which each cobalt center exhibited a distorted square pyramidal geometry. Among the prepared complexes, Co1 demonstrated the highest catalytic activity of 1.37 × 105 g (mol of Co)−1(h)−1, achieving complete monomer conversion and resultant polyisoprene showed high molecular weight (Mn ≥ 2.6 × 105 g/mol). All of the complexes showed preference for the cis-1,4 configuration ranging from 65% to 72%, while the 3,4 monomer insertion units constituted between 27% and 34% of the polymer structure. Moreover, extensive investigations were conducted to assess the impact of reaction parameters and ligand properties on the catalytic activities and microstructural characteristics of the resulting polymer.

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