Regioselectivity Study on Propylene Polymerization Catalyzed by Neutral Salicyladiminato Pd（Ⅱ） Model Complex with DFT Method

Many attempts have been made to control the regioselectivity for olefin polymerization by varying the structures of ligands in catalysts. The regioselectivity of propylene polymerization was investigated by replacing a nitrogen atom in the Pd(Ⅱ) diimine catalyst with an oxygen atom from density functional theory method at the B3LYP/LANL2DZ level. The results show that the 1,2-insertion becomes a rival mechanism to the 2,1-insertion when the nitrogen atom is replaced by the oxygen atom leading to an asymmetric environment in the catalyst, and that the steric effect in the asymmetrical catalyst plays an important part in the polymerization. The insertion barrier from 2-O is much higher than that from 2-N. A pyramid transition state was characterized for the catalyst to convert 2-O back to 2-N through internal rotation. The propylene prefers to coordinate at the opposite side of O in the catalyst. This is the driving force for the internal rotation.The results are significant for isotactic and syndiotactic polymerization.     

硼掺杂拓扑绝缘体Bi2Se3单晶的电输运性质研究

本文首次报道了用自助溶剂法(self-flux)制备优良的硼(B)掺杂硒化铋(Bi2BxSe3-x)样品的探索。实验结果显示掺杂样品中大部分B是以替代Se位方式存在,少量B以插入Bi2Se3晶格或范德瓦尔斯间隙的形式存在。当B的含量逐渐增加时,Bi2Se3的晶格常数c先减小后增加,且样品具有清晰的层状结构。掺杂量x=0.05的样品局部区域出现纳米带结构,同时该样品在低温下出现了明显的金属-绝缘转变现象。Bi2Se3样品电阻率随掺杂含量的增加而增加,表明B掺杂提高了样品表面态对整体电导的贡献,同时纳米带结构也有助于增加表面态的贡献。