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: HL1 = pyridine-2-aldoxime; Fe2: HL2 = 6-methylpyridine-2-aldoxime; Fe3: HL3 = phenyl-2-pyridylketoxime; Fe4: HL4 = 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 HL2. 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 x 10(6) g/mol center dot 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 [Ph3C][B(C6F5)(4)]/AlR3 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.

Automated summary

Iron complexes with different pyridine-oxime ligands were synthesized and characterized. The crystal structure of one complex was determined, demonstrating the coordination mode of the pyridine-oxime ligands. The complexes showed high catalytic activity in the polymerization of isoprene.