Synthesis, Characterization and Catalytic Property Studies for Isoprene Polymerization of Iron Complexes Bearing Unionized Pyridine-Oxime Ligands

Iron complexes of the types [Fe(HL)(2)Cl(2)] (Fe1: HL(1) = pyridine-2-aldoxime; Fe2: HL(2) = 6-methylpyridine-2-aldoxime; Fe3: HL(3) = phenyl-2-pyridylketoxime; Fe4: HL(4) = picolinaldehyde O-methyl oxime) were prepared and characterized by elemental analysis and IR spectroscopy. The crystal structure of Fe2, determined by single-crystal X-ray diffraction, featured a distorted octahedral coordination of the iron center binding with two ligands of HL(2). The X-ray structure and infrared spectral data indicated that pyridine-oxime ligands act as unionized bidentate ligand by coordinating with N(pyridine) and N(oxime). The catalytic performance for isoprene polymerization, catalyzed by these pyridine-oxime-ligated iron complexes, was examined. For a binary catalytic system combined with MAO, complexes Fe1, Fe3 and Fe4 were found to be highly active (up to 6.5 × 10(6) g/mol·h) in cis-1,4-alt-3,4 enchained polymerization, with average molecular weights in the range of 60–653 kg/mol and narrow PDI values of 1.7–3.5, even with very low amounts of MAO (Al/Fe = 5). Upon activation with [Ph(3)C][B(C(6)F(5))(4)]/AlR(3) for the ternary catalytic system, theses complexes showed extremely high activities, as well about 98% yield after 2 min, to afford cis-1,4-alt-3,4-polyisoprene with a molecular weight of 140–420 kg/mol.