DFT mechanistic study of the H2‐assisted chain transfer copolymerization of propylene and p‐methylstyrene catalyzed by zirconocene complex

DFT computations have been performed to investigate the mechanism of H₂‐assisted chain transfer strategy to functionalize polypropylene via Zr‐catalyzed copolymerization of propylene and p‐methylstyrene (pMS). The study unveils the following: (i) propylene prefers 1,2‐insertion over 2,1‐insertion both kinetically and thermodynamically, explaining the observed 1,2‐insertion regioselectivity for propylene insertion. (ii) The 2,1‐inserion of pMS is kinetically less favorable but thermodynamically more favorable than 1,2‐insertion. The observation of 2,1‐insertion pMS at the end of polymer chain is due to thermodynamic control and that the barrier difference between the two insertion modes become smaller as the chain length becomes longer. (iii) The pMS insertion results in much higher barriers for subsequent either propylene or pMS insertion, which causes deactivation of the catalytic system. (iv) Small H₂ can react with the deactivated [Zr]?pMS?PP_n facilely, which displace functionalized pMS?PP_n chain and regenerate [Zr]? H active catalyst to continue copolymerization. The effects of counterions are also discussed. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 576–585     

Divergent Synthesis of Oxa-Cyclic Nitrones through Gold(I)-Catalyzed 1,3-Azaprotio Transfer of Propargylic α-Ketocarboxylate Oximes: Experimental and DFT Studies

1,3-Azaprotio transfer of propargylic α-ketocarboxylate oximes, a new type of alkynyl oximes featuring an ester tether, has been explored by taking advantage of gold catalysis. The incorporation of an oxygen atom to the chain of alkynyl oximes led to the formation of two different oxa-cyclic nitrones. It was found that internal alkynyl oximes with an E-configuration deliver five-membered nitrones, whereas terminal alkynyl oximes with an E-configuration afford six-membered nitrones. DFT calculations on four possible pathways supported a stepwise formation of C−N and C−H bonds, in which a 1,3-acyloxy-migration competes with the 1,3-azaprotio-transfer, especially in the case of internal alkynyl oximes. The relative nucleophilic properties of oxygen in the carbonyl group and the nitrogen in the oxime, the electronic effects of alkynes, and the influence of the ring system have been investigated computationally.     

Directing-Group-Free C7-Alkylations of N-Alkylindoles Mediated by Cationic Zirconium Complexes: Role of Brønsted Acid for Catalytic Manifold

Highly position selective alkylations of N-alkylindoles at C7-positions have been enabled by cationic zirconium complexes. The strategy provides a straightforward access to install alkyl groups at C7-positions of indoles without a complex directing group. Mechanistic studies provided support for the importance of Brønsted acids in the catalytic manifold.     

项目引入法——可普遍采用的研究性学习模式

研究性学习是实施素质教育和创新教育的一种新型教学方式。在工科类课程的教学中 可采用引入一个工程项目,通过项目设计来学习研究新知识,完成教学计划。     

梯度网络平稳点集合的Hopfield稳定性与吸引域

给出梯度神经网络模型的电路实现 ,证明了网络平稳点集合的全局 Hopfield稳定性。对各个平稳点吸引域的几何估计得到了相关结果 ,这为网络初始输入的数量与方向判定提供了基本的量度参数准则。     

利用有限元法进行塔机起重臂的动态分析

根据塔机起重臂的实际结构 ,建立双弹簧悬吊超静定简支梁的力学模型 ,进行动态分析 ,并以TC80型塔式起重机为例 ,利用有限元方法求解 ,引入梁单元和边界单元 ,得到塔机起重臂的多阶固有频率和主振型 ,其结果对于塔机的动态响应分析具有实际意义     

给水处理系统高效经济运行的生产性评价

研究给水处理系统的高效经济运行技术 ,是保证水厂高效、安全、经济供水的重要措施 .生产运行实践证明 ,采用高效经济方式运行的确可以节约可变费用 .尤其是在冬季低温低浊水的净化中 ,可变费用的节约程度最高可达 2 0 %以上     

中国教育如何应对WTO的挑战

加入WTO将对我国生产力的发展和高等教育事业产生重大而深远的影响。文章分析了中国加入WTO后教育面临的挑战和机遇，研究和探讨了教育应对WTO的对策。     

物流系统容错设计方法

在相关理论的指导下，提出了物流容错技术的基本概念，论述了常见的系统故障、典型的容错设计方法和故障检测手段，讨论了物流容错技术的应用前景和发展方向。