Synthesis, Structure And Characterization Of Substituted Indenyllanthanide Complexes And Their Catalytic Activity For Polymerization Of Polar Monomers

This article describes the syntheses and characterization of a series of substituted indenyl lanthanide divalent complexes, chloride and amides, including (1-C5H9C9H6)2Ln(THF)n(Ln = Sm, n = 1; Ln = Eu, Yb, n = 2), KSm(1-C5H9C9H6)3(THF)3, (1-PhCH2C9H6)2Ln(THF)2 (Ln = Sm, Eu), (1-PhCH2C9H6)2Sm(THF)2, [(NaC9H6)Me2CC5H4]2Sm(THF)2,(C5H9C9H6)2Y( -Cl)2Li(THF)2, (1-PhCH2C9H6)2SmNPh2 and (C5H9C9H6)2YN(SiMe3)2. The crystal structures of the two complexes (1-C5H9C9H6)2Yb(THF)2 and (C5H9C9H6)2Y( -Cl)2Li(THF)2 were determined by X-ray diffractometer. The catalytic activity for the above complexes except (C5H9C9H6)2Y( -Cl)2Li(THF)2, (1-C5H9C9H6)2Eu(THF)2 and (1-PhCH2C9H6)2Eu(THF)2 were tested and it is found that the substituted indenyl complexes of divalent lanthanide elements could be shown good catalytic activity in the polymerization of methyl methacrylate (MMA), dimethylamino ethyl methacrylate(DMAEMA), the copolymerization of MMA and DMAEMA and the ring opening polymerization of -caprolactone as well. The substituted indenyl lanthanide divalent complexes together with quaternaries can also catalyze the polymerization of acrylonitrile;1. The reaction between K(1-C5H9C9H6) and anhydrous LnCl3 (Ln = Sm, Eu, Yb) in 2:1 molar ratio in THF with subsequent treatment by Na-K alloy afforded (1-C5H9C9H9)2Ln(THF)n (Ln = Sm, n = 1; Ln = Eu, Yb, n = 2). The reaction of SmI2 with K(1-C5H9C9H6) in 1:2 molar ratio in THF gave the anionic complex KSm(l-C5H9C9H6)3(THF)3. The complexes all were characterized by elemental analysis, IR and X-ray crystal structural analysis for?(1-C5H9C9H6)2Yb(THF)2.2. The reaction between K(1-PhCH2C9H6) and anhydrous EuCl3 in 2:1 molar ratio in THF with subsequent treatment by Na-K alloy afforded (1-PhCH2C9H6)2Eu(THF)2. The reaction of SmI2 with K(1-PhCH2C9H6) in 1:2 molar ratio in THF gave complex (1-PhCH2C9H6)2Sm(THF)2. The complexes both were characterized by elemental analysis and IR.3. The reaction of SmI2 with K(1-CH3CH2C9H6) in 1:2 molar ratio in THF gave complex1-PhCH2C9H6(THF)2. The complex was characterized by elemental analysis and IR. 4. The reaction of Li(1-CsHgCgHe) and anhydrous YCla in 2:1 molar ratio in THF gave the anionic complex (CsHgCgH6)2Y( -Cl)LiCTHF)2, which was characterized by elemental analysis, IR and X-ray crystal structural analysis. It is the first substituted-indenyl rare earth chloride determined by X-ray structural analysis.5. Complexes (l-PhCH2C9H6)2SmNPh2 and (CsHgCgH)YNCSiMesh have been successfully synthesized by the reaction of alkali metal amides with substituted indenyl lanthanide chlorides and were characterized by elemental analysis, IR and !H NMR.6. The catalytic activity of the above lanthanide(II) complexes was studied for the polymerization of MMA. The results indicated that these complexes show good catalytic activity and the catalytic activity affected by the temperature and time of polymerization, amount of catalyst used and the solvent as well. The polymerization gives syndiotacticity-rich PMMA.7. The complex (l-C5HgCgHehYtyTHF)2 is first found to be able to initiate the polymerization of DMAEMA. The catalytic activity depends on the temperature and time of polymerization, amount of catalyst and the solvent. The polymerization gives the poly DMAEMA syndiotacticity-rich. The substituted indenyllanthanide(II) complexes tested all show good catalytic activity for the polymerization of DMAEMA.8. The substituted indenyllanthanide(II) complexes tested all show good catalytic activity for the copolymerization of DMAEMA and MMA. The catalytic activity was affected by the temperature and time of polymerization, amount of catalyst and the solvent.9. The polymerization of acrylonitrile catalyzed by substituted indenyl lanthanide(II) complexes/additive system was studied. It was found that quaternaries and sodium aryloxide are good additives for acrylonitrile polymerization. All the catalyst systems consiste...