Synthesis And Characterization Of Organolanthanide Amides And Their Catalytic Behavior For Polymerization

Eight organolanthanide complexes supported by nitrogen-based ligands guanidinates and arylamides were first synthesized and well characterized. Further X-ray diffraction revealed structural features of 5 complexes. The catalytic behaviors of some organolanthanide complexes for homopolymerizations and copolymerizations of s-CL, TMC, MMA were investigated.1. Homoleptic guanidinate lanthanide complexes [Ph2NC(NCy)2]3Yb-2C7H8(l), [Ph2NC(NCy)2]3Nd-2C7H8(2),[Ph2NC(NCy)2]3Sm-2C7H8(3)and [Ph2NC(N'Pr)2]3Sm(4) were prepared in good yield by the metathesis reaction or the insertion reaction. All these complexes were characterized by elemental analysis, IR spectroscopy, 1H NMR spectroscopy, and the molecular structures of complexes 1, 2 and 3 were further determined by X-ray diffraction.2. Organolanthanide complexes supported by arylamides ligands [(C6H3-/Pr2-2,6)(Me3Si)N]2YCl2Li(TMEDA)(5), [(C6H3-'Pr2-2,6)(Me3Si)N]2Yb (N'Pr2)ClLi(THF)3(6), {[Ph(Me3Si)N]2YbCl(THF)}2-C7H8(7) and [Ph(Me3Si)N]3Yb(THF)(8) were synthesized and characterized by elemental analysis, IR spectroscopy, 1H NMR spectroscopy, and the molecular structures of complexes 6 and 7 were further determined by X-ray diffraction.3. It was found that homoleptic guanidinate lanthanide complexes are efficiently single-component initiators for the ring-opening polymerization of TMC. Effect of temperature, time and the structure of catalysts on the polymerization were studied. The polymerization mechanism was also investigated.4. The polymerizations of TMC, s-CL and MMA initiated by complexes 7 and 8 were tested primarily.