Rh complexes of 1-(2,4,6-triisopropylphenyl-)3-methyl-1H-phosphole: preparation and use as catalysts in the hydroformylation of styrene

In the series of 1-(2,4,6-trialkylphenyl-)3-methyl-1H-phospholes (1a–c) that are to a certain extent of aromaticity, only the isopropyl substituted one (1a) entered into reaction with dimeric (pentamethylcyclopentadienyl)rhodium dichloride to afford Rh(III) complex (2a) in a reversible manner. After a careful workup, (2a) could be prepared and characterized whose stereostructure was elucidated by B3LYP/3–21G*, B3LYP/6–31G* and LANL2DZ calculations. Complex (2a) as a preformed catalyst, as well as the Rh(acac)(CO)₂ + 2(1a) in situ catalytic system were useful in the hydroformylation of styrene and gave the branched aldehyde in regioselectivities of 65–96%.     

含锆层柱蒙脱石对1,2,4三甲基苯歧化反应的催化作用

用离子共聚法合成了硅锆层柱蒙脱石（ＳｉＺｒＰＩＬＭ）和铁锆层柱蒙脱石（ＦｅＺｒＰＩＬＭ），考察了它们对１，２，４三甲基苯（１，２，４ＴｒＭＢ）歧化反应的催化性能．１，２，４ＴｒＭＢ在催化剂样品上可发生歧化反应和异构化反应，歧化反应选择性达８０％以上．随着催化剂预处理温度的提高，１，２，４ＴｒＭＢ转化率下降，歧化反应选择性和四甲基苯（ＴｅＭＢ）中１，２，４，５ＴｅＭＢ含量则升高．催化剂对１，２，４ＴｒＭＢ歧化反应有择形催化作用，１，２，４，５ＴｅＭＢ和间二甲苯、邻二甲苯为主要产物，并且其含量偏离其热力学平衡组成，ＴｅＭＢ中１，２，４，５ＴｅＭＢ的含量在８５％以上．     

硫酸氢铵分解动力学及其分解机理的研究

为了筛选适合的化学贮能系统,Wentworth等人曾提出了十项筛选标准。照此标准衡量,硫酸氢铵的分解-合成反应是一个十分理想的贮能系统: NH_4HSO_4(l)?NH_3(g)+H_2(g)+SO_3(g)Prengle也曾就此反应应用于太阳能电站贮能系统的可行性作过理论上的探讨.但是,有关该反应的基础研究进行的还很不够,特别有关分解动力学和分解机理的研究文献尚未见报导。本文用等温热重法和程序升温热重法对硫酸氢铵的热分解动力学进行了研究,并确定了分解机理,为贮能系统的实际应用提供了基础数据。     

New catalytic effect of thiourea on the oxidative cyanation of N-aryltetrahydroisoquinolines

Thiourea itself has been introduced as a mild and efficient organocatalyst for the oxidative α -cyanation of N-aryltetrahydroisoquinolines (THIQs) with trimethylsilyl cyanide (TMSCN), giving the corresponding products in good to excellent yields. Experimental investigations demonstrated that thiourea acts as a radical initiator by abstracting hydroxyl radical (OH) from tert-butyl hydroperoxide (TBHP) directly instead of non-covalent hydrogen bondings (H-bondings) activation. The use of thiourea as a radical initiator offers a new avenue for innovative chemical transformations in organocatalyzed radical chemistry.     

Electronic stopping powers of Ni, Gd and Pd metals for 19F ions at low energy

Summary Electronic stopping power of ¹⁹F in Ni, Pd and Gd was measured and compared to Mstar and SRIM calculation as well as experimental results published in literature. It turns out that the present electronic stopping power agrees reasonably well with them.     

奋乃静和氟奋乃静的毛细管电泳柱端喷壁式安培检测

应用自组装毛细管电泳．安培检测装置，建立了同时分离检测抗精神病药奋乃静与氟奋乃静的新方法。在1050mV(vs．Ag／AgCl)检测电位下，奋乃静与氟奋乃静的检出限分别达0．060mg／L与0．075mg／L。在最佳检测条件下，两组分的响应电流与浓度之间有着良好的线性关系，线性范围为0．75～75mg／L。将方法用于药物片剂以及模拟尿样和血清样品中奋乃静和氟奋乃静的测定，结果令人满意。     

关于meso—四苯基卟啉在冰醋酸中的存在形式

前言卟啉在生物化学、分析化学、药物化学等领域有着广泛研究和重要应用［１～３］。近年来虽然对卟啉类化合物的研究报道很多［４～６］，但对卟啉在酸性介质中的研究很少。较早期的研究工作认为卟啉类化合物在酸性介质中仅以其二酸形式存在［７］。本文实验结果显示ｍｅ...     

Achieving ‘Desirable and Feasible’ Change: An Application of Soft Systems Methodology

Rational intervention in human affairs, if it is to constitute not only action but also research, so that future interventions may be made more effective, needs a well-defined methodological framework. Soft systems methodology (S.S.M.) provides one such framework. S.S.M. is doubly systemic: it is itself a learning system, and within that system it uses systems models, models of human activity systems. It accepts that such models are not models of parts of the real world, only models of ways of perceiving the real world, that is to say, models relevant to debate about ‘reality’ (one man's ‘terrorism’ is another's ‘freedom fighting’).S.S.M. is here illustrated by means of an account of a systems study of change in the information function of a sophisticated science-based company. The study is described from the point of view of a professional analyst who was helping a team of three managers carry out the study. The course of the study is described, and a separate commentary relates its activity to the seven stages of S.S.M. The study involved three cycles round stages 2–3–4–5 of S.S.M., the stages in which models of relevant human activity systems are built and compared with the real world in order to construct a rich debate about changes whose introduction in the problem situation world be both (systemically) desirable and (culturally) feasible.     

钙钛矿型La_((1 x)/2)Sr_((1-x)/2)Co_(1-x)Cu_xO_3催化CO氧化活性与表征

研究了钙钛矿型LaSrCoCu_xO_3催化剂对CO氧化反应的催化活性及其表面氧的催化作用．结果表明，x＝0．4的催化剂对CO氧化具有最高催化活性，常压及本实验条件下CO完全氧化的最低温度为168℃；催化剂均为氧缺陷化合物，吸附于表面晶格氧缺陷上的吸附氧是CO氧化反应的活性氧物种；并发现催化剂中存在有非常价态的C04 ，认为CO氧化反应是通过吸附氧调变Co3 和Co4 价态而进行．