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研究了双组分体系Cp3Ln/HSCH2CH2NEt2(Ln=Sm,Yb)催化ε-己内酯聚合反应性能,并与Cp3Ln/HOCH2CH2NMe2和Cp3Ln(Ln=Sm,Yb)催化结果进行了比较,发现催化活性:Cp3Yb/HOCH2CH2NMe2>Cp3Sm/HOCH2CH2NMe2>Cp3Yb/HSCH2CH2NEt2>Cp3Sm/HSCH2CH2NEt2>Cp3Sm>Cp3Yb。发现Cp3Ln(Ln=Sm,Yb)和HSCH2CH2NEt2是通过可逆平衡反应生成相应茂基稀土硫化物的,硫醇的加入可提高Cp3Ln的催化活性。Cp3Ln(Ln=Sm,Yb)和HOCH2CH2NMe2反应则立即完全生成茂基稀土烷氧化合物。测定了[Cp2Sm(μ-OCH2CH2NMe2)]2的晶体结构。
The catalytic performance of the two-component systems Cp3Ln / HSCH2CH2NEt2 (Ln = Sm, Yb) catalyzed by ε-caprolactone was studied and compared with the catalytic results of Cp3Ln / HOCH2CH2NMe2 and Cp3Ln (Ln = Sm, Yb) Cp3Yb / HOCH2CH2NMe2> Cp3Sm / HOCH2CH2NMe2> Cp3Yb / HSCH2CH2NEt2> Cp3Sm / HSCH2CH2NEt2> Cp3Sm> Cp3Yb. It was found that Cp3Ln (Ln = Sm, Yb) and HSCH2CH2NEt2 are produced by reversible equilibrium reaction of the corresponding cyclopentadienyl sulfide. The addition of mercaptans increases the catalytic activity of Cp3Ln. The reaction of Cp3Ln (Ln = Sm, Yb) with HOCH2CH2NMe2 immediately led to the complete formation of the Maukane Rare Earth Alkoxide. The crystal structure of [Cp2Sm (μ-OCH2CH2NMe2)] 2 was measured.