Influences of Fluorine Substituents on Iminopyridine Fe(II)- and Co(II)-Catalyzed Isoprene Polymerization

A series of iminopyridine complexes of Fe(II) and Co(II) complexes bearing fluorinated aryl substituents were synthesized for the polymerization of isoprene. The structures of complexes3a,2band3bwere determined by X-ray diffraction analysis. Complex3acontained two iminopyridine ligands coordinated to the iron metal center forming an octahedral geometry, whereas2badopted a chloro-bridged dimer, and3bfeatured with two patterns of cobalt centers bridged via chlorine atoms. Complexes2band3brepresented rare examples of chlorine bridged bimetallic Co(II) complexes. The fluorine substituents effects, particularly on catalytic activity and polymer properties such as molecular weight and regio-/stereo-selectivity were investigated when these complexes were employed for isoprene polymerization. Among the Fe(II)/methylaluminoxane (MAO) systems, the 4-CF3substituted iminopyridine Fe(II) complex1awas found as a highly active isoprene polymerization catalyst exhibiting the highest activity of 106g·(mol of Fe)−1·h−1. The resultant polymer displayed lower molecular weight (Mn= 3.5 × 104g/mol) and moderate polydispersity index (PDI = 2.1). Furthermore, the ratio ofcis-1,4-/3,4 was not affected by the F substituents. In the series of Co(II)/AlEt2Cl binary systems, complexes containing electron-withdrawing N-aryl substituents (R = 4-CF3, 2,6-2F) afforded higher molecular weights polyisoprene than that was obtained by the complex containing electron-donating N-alkyl substituents (R = octyl). However, ternary components system, complex/MAO/[Ph3C][B(C6F5)4] resulted in low molecular weight polyisoprene (Mn< 2000) with hightrans-1,4-unit (>95%).Keywords:iminopyridine ligands;Fe(II);Co(II) complexes;isoprene polymerization;fluorinated aryl substituents