Synthesis Of Rare Earth Complexes Of The New ¦Ð Ancillary Ligands And Their Catalytic Performance

By using Me2C(Ind)(Cp)Li2 and [(C9H7)Me2C]CpLi as -ligands, a series of ansa-lanthanocene complexes have been synthesized and characterized in the first time. Their catalytic activities for polar monomers such as MilvIA were also studied. 1. Two ansa-lanthanocene chlorides were synthesized by the equimolar reaction of Me2C(Ind)(Cp)Li2 with anhydrous LnCI3 (Ln = Nd and Sm). Their structures were verified by elemental analyses and IR spectroscopy. 2. Me2C(Ind)(Cp)Li2 reacted with anhydrous LnC13 (Ln = Y, Gd, and Yb) at room temperature in TI-IF with subsequent reaction with KNPh2 gave the corresponding diphenylami de derivative ansa-Me2C(Ind)(Cp)LnNPh2(TI-IF) (Ln Y~ Gd, and Yb) . All these complexes were verified by elemental analyses and JR spectroscopy. For Y complex, -LNMIR spectra was also determined. 3. The equimolar reaction of Me2C(Ind)(Cp)Li2 with Sm12 gave the corresponding Sm(II) complex, ansa-Me2C(Ind)(Cp)Sm (TI-if)2. Its structure was verified by elemental analyses and JR spectroscopy. 4. The reaction between [(C9H7)Me2C]CpLi and anhydrous SmC13 in 2:1 molar ratio with subsequent reduction by sodium sand in 3:1 molar ratio of Sm to Na in THE gave a new bimetallic complex [(N& - Ind)Me2CCp]2Sm(THF)2 ( Ind=C9H6, indenyl). The complex was identified by elemental analysis, JR spectroscopy. 5. The catalytic activity of ansa-Me2C(Ind)(Cp)LnNPh2(THIF) (Ln Y, Gd, Yb) was tested. The results indicated that these ansa-lanthanocene amides were active for the polymerization of methyl rnethacrylate(MIMA) in toluene. But the conversions were not high and the temperature of polymerization influenced the conversions obviously. 6. We also investigated the catalytic behavior of the new bimetallic complex [(Na ind)Me2CCp]2Sm(THF)2 for M1MA polymerization in detail. The results indicated that [(Na ind)Me2CCp]2Sm(THIF)2 exhibited good catalytic activity in the polymerization of MIMA, affording iso-rich poly(MIMA)s. Moreover, indenylsodium of [(Na Ind)Me2CCp]2Sm(THIF)2 only exhibited much low catalytic activity in the polymerization of MIMA. 7. The catalytic activity of the bimetallic complex [(Na ind)Me2CCp]2Sm (TI-IF)2 for DMAEMA and AN was also investigated. The preliminary results indicated that [(Na ind)Me2CCp]2Sm(THF)2 could initiate the polymerization of DMAEMA and AN. We found that the conversion of AN would increase greatly when a little amount of CH3(CH915N(CH3)3Br was added into the polymerization systems. Gong Xinqiang Directed by?Professor Shen Qi...