Theoretical Investigation of the Mechanism of Rh(III)-catalyzed Annulation of 2-Biphenylboronic Acid with Activated Alkene

The mechanism is investigated for Cp^tBuRh(OH)₂-catalyzed annulation of 2-biphenylboronic acid with three activated alkenes using M06-2X functional. The reaction comprises transmetalation via two steps and following C-H activation producing reactive Rh-biphenyl complex with two Rh—C σ bonds. After the coordination/insertion of alkenes, respective fused or bridged cyclic products are yielded depending on different alkenes accompanied by the release of Cp^tBuRh. The promotion of Cp^tBuRh(OH)₂ lies in the barrier decrease of transmetalation and C-H activation ready for coordination/insertion ensuring the smooth progress of common rate-limiting reductive elimination. The stereoselective transfer and ring rotation are specific for benzoquinone and cyclopropenone. The role of Rh(III) catalyst and release of Rh(I) is supported by Multiwfn analysis on frontier molecular orbital(FMO) of specific transiton states(TSs) and Mayer bond order(MBO) value of vital bonding, breaking.     

[Zn(phen)3]·2Bsesa·4H2O配合物的合成及其晶体结构

在水醇溶液中合成了配合物[Zn(phen)3]·2Bsesa·4H2O(1,phen=邻菲咯啉,BsesaH=苯磺酰牛磺酸),其结构经IR,元素分析和X-射线衍射表征.1属三斜晶系,P-1空间群,晶胞参数:a=1.111 5(3)nm,b=1.415 5(4)nm,c=1.748 6(5)nm,α=80.764(5)°,β=87.237(5)°,γ=88.081(5)°,V=2.711 3(14)nm3,Z=2,Dc=1.478 g·cm-3,μ=0.681 mm-1,F(000)=1 252.1为变形的八面体构型,Zn(Ⅱ)与3个邻菲咯啉配位,未与苯磺酰牛磺酸中的氧原子配位.     

乙醇/水混合溶剂中Gemini表面活性剂的表面性质

通过对Gemini表面活性剂12-s-12 (Et)(s=4, 6, 8, 10, 12)体系在乙醇/水混合溶剂中的表面张力曲线的测定, 对该体系的表面性质进行了研究. 发现随乙醇/水比例变化, Gemini各种表面化学性质, 如临界胶束浓度(cmc)、表面张力(γcmc)、饱和吸附量(Γmax)和最小分子占有面积(Amin)等的变化规律. 拓展了Gemini表面活性剂在混合溶剂中表面吸附的研究.     

求解Euler方程的区域分解方法与并行算法

将复杂形状区域划分成多块子区域,研究发展了一种多块区域之间迎风守恒型的内边界耦合方法,实现相邻子区域解的光滑过渡,使多区耦合得到总体流场的数值解。对二维翼型跨音速流动和圆弧形隆起物超音速流动等进行了分区数值计算,并将计算结果与单区计算结果和实验结果作了比较。并行分区计算引入"先进先出"的同步控制等待机制,实现了高效率并行计算,还分析了影响并行效率的主要因素。     

1a,3-二苯基-1,1,4,4-四氯-1a,2,3,4-四氢-1H-吖丙啶并[2,1-e][1,6]苯并硫氮杂辛因的合成及晶体结构

苯并杂类化合物为常用镇静剂及治疗心血管疾病和抗病毒的药物［１～３］,苯并杂与五六元杂环并合形成的三环化合物也是重要的药用杂环化合物,如１,４－苯并二氮杂与１,２,４－三唑并合形成的三环化合物为常用的治疗中枢神经系统疾病药物［４］．而吖丙啶与１,...     

First Total Synthesis of (-)-4-O-(6'-Hydroxy-7'(9')-Dehydro-6',7,-Dihydrogeranyl)-Coniferyl Alcohol

Some Ligularia species have long used as folk remedies due to their antibiotic, antiphlogistic and antitumor activities.¹ Compound 1,² a novel coniferyl alcohol, was isolated from ligularia duciformis(Compoitae). The geometrical structure of 1,determined by spectroscopic techniques, was corresponded to 4-o-(6,-hydroxy-7'(9')-dehydro-6',7'-dihydrogeranyl)-coniferyl alcohol. But its absolute configuration at C-₆,has not yet been determined. Herein, we report the total synthesis of (6'S)-(-)-1 from Geraniol 2 through 9 steps (Scheme 1).     

磺化酞菁镓的二聚现象研究

采用分光光度法研究了磺化酞菁镓的二聚现象;测定了二聚常数k_d,讨论了PH值、离子强度、水、温度等因素对k_d的影响,研究结果表明:磺化酞菁镓的二聚反应可表示成:2SPcGaOH⇔(SPcGa)₂O+H₂O 且磺化酞菁镓的二聚常数随着离子强度、磺酸基数目、水的浓度的增加而增加。     

气液色谱法研究二元混合固定液的无限稀活度系数

用气液色谱法测定若干烃类溶质在二元混合固定液中的无限稀活度系数,所研究的二元混合液为具有不同极性的四种类型:(1)正廿二烷-正十六烷;(2)邻苯二甲酸二壬酯-角鲨烷;(3)环丁砜-碳酸丙烯酯;(4)环丁砜-己二腈。用最小二乘法拟合三元系的Flory-Huggins公式,得到各种相互作用参数。     

三硼酸铯和硼酸铯锂晶体的晶格振动光谱研究

本文对新型非线性光学晶体三硼酸铯（ＣｓＢ３Ｏ５∶ＣＢＯ）和硼酸铯锂（ＣｓＬｉＢ６Ｏ１０∶ＣＬＢＯ）进行了晶格振动光谱研究。首先对两种晶体的基本晶格振动模进行了对称性分类,记录了两种晶体低温下的拉曼光谱和室温下的红外反射光谱,对晶体的晶格振动模进行了认定,将振动模归属于平面六元环（Ｂ３Ｏ６）和四面体（ＢＯ４）。然后比较了ＣＢＯ,ＣＬＢＯ和ＬＢＯ（ＬｉＢ３Ｏ５）三种晶体的晶格振动光谱,讨论了阳离子对振动光谱的影响。另外,还讨论了硼酸盐晶体晶格振动模ＬＯ ＴＯ分裂的大小与晶体非线性光学系数之间的关系。