钐(Ⅱ)类卡宾CH_3SmCH_2X(X=Cl、Br和Ⅰ)促进乙烯环丙烷化反应途径的理论研究(英文)

用密度泛函B3LYP方法研究了过渡金属钐类卡宾与乙烯的环丙烷化反应的机理。对三种不同的钐的SS试剂CH_3SmCH_2X(其中X=Cl、Br和Ⅰ)分别和CH_2CH_2反应的各反应物、中间体、过渡态和产物构型的全部结构几何参数进行了优化,用内禀反应坐标(IRC)计算和频率分析方法,对过渡态进行了验证。结果表明：CH_3SmCH_2X(其中X=Cl、Br和Ⅰ)与CH_2CH_2环丙烷化反应按亚甲基转移通道(通道A)和卡宾金属化通道(通道B)都可以进行,与锂类卡宾的反应机理相同,只是按亚甲基转移通道(通道A)进行反应较容易一些,而且此反应在较低的温度下就可以发生。     

A CLASS OF r-POINT (r+1)ST-ORDER A-STABLE ONE-BLOCK METHODS WITH DAMPING AT THE INFINITE POINT

1　ＩｎｔｒｏｄｕｃｔｉｏｎＦｏｒｓｏｌｖｉｎｇｓｔｉｆｆｉｎｉｔｉａｌｖａｌｕｅｐｒｏｂｌｅｍｓｆｏｒｓｙｓｔｅｍｓｏｆＯＤＥｓｙ′=ｆ(ｙ) ,ｙ(ｔ0 ) =ｙ0 ,ｔ0 <ｔ≤Ｔ ,ｙ0 ,ｙ∈Ｒｍ,ｆ :Ω Ｒｍ →Ｒｍ (1 .1 )ｍａｎｙｐａｒｔｉｃｕｌａｒｏｎｅ ｂｌｏｃｋｍｅｔｈｏｄｓｏｆｔｈｅｆｏｒｍＹｎ+1= ＡＹｎ+ｈ( Ｂ0 Ｆ(Ｙｎ) + Ｂ1Ｆ(Ｙｎ+1) ) , Ａ =Ａ Ｉｍ, Ｂｉ=Ｂｉ Ｉｍ,Ａ ,Ｂｉ∈Ｒｒ×ｒ,Ｙｎ =(ＹＴｎｒ,… ,ｙＴ(ｎ+1)ｒ- 1) Ｔ,Ｆ(Ｙｎ) =(ｆＴ(ｙｎｒ) ,… ,ｆＴ(ｙ(ｎ+1)ｒ- 1) ) Ｔ,ｙｊ≈ ｙ(ｔｊ) ,…     

混杂配体金属簇合物的分子振动光谱与结构

由于原子簇化合物在催化，生物活性，功能材料等方面所呈现的重要性，使其成为无机和物理化学最重要的研究领域之一。文章中和谱学方法对一些具有混配体的过渡金属簇合物的结构及其两者之间的关系进行.     

HIGH ACCURACY FINITE VOLUME ELEMENT METHOD FOR TWO-POINT BOUNDARY VALUE PROBLEM OF SECOND ORDER ORDINARY DIFFERENTIAL EQUATIONS

1　ＩｎｔｒｏｄｕｃｔｉｏｎＦｉｎｉｔｅｖｏｌｕｍｅｅｌｅｍｅｎｔｍｅｔｈｏｄｏｒＦＶＥＭｕｓｅｓａｖｏｌｕｍｅｉｎｔｅｇｒａｌｆｏｒｍｕｌａｔｉｏｎｏｆｔｈｅｄｉｆ ｆｅｒｅｎｔｉａｌｅｑｕａｔｉｏｎｗｉｔｈａｆｉｎｉｔｅｐａｒｔｉｔｉｏｎｉｎｇｓｅｔｏｆｖｏｌｕｍｅｔｏｄｉｓｃｒｅｔｉｚｅｔｈｅｅｑｕａｔｉｏｎ ,ｔｈｅｎｒｅ ｓｔｒｉｃｔｓｔｈｅａｄｍｉｓｓｉｂｌｅｆｕｎｃｔｉｏｎｓｔｏａｌｉｎｅａｒｆｉｎｉｔｅｅｌｅｍｅｎｔｓｐａｃｅｔｏｄｉｓｃｒｅｔｉｚｅｔｈｅｓｏｌｕｔｉｏｎ ([1 -4 ] ) .…     

OXIDATION OF TiAl,Ni AND Fe IN A DYNAMIC ENVIRONMENTAL SEM

IntroductionInmaterialscience,differentmicrostructuresofthesamematerialsmayinducediversebehaviorsanddifferentcharacteristics.Westwood(1988)showed,asanexample,thatthetreatmentofaluminumsurfacewithcommercialphosphoricacidproducedmechanicallyinterlockedoxide搘hiskers?approximately10nmindiameterand400nminlength,whichmechanicallyinterlocked.Thismicro-structurecankeepsuchaconglomeratebondedoverconsiderablerangesofstressandtemperature.Inahumidatmosphere,especiallythatcontainingchlorine,however,suchox…     

利用电泳技术在不锈钢和铁基底上制备MgB2带材

本文首次报道了利用电泳技术在铁和不锈钢基底上制备MgB2超导带材.电阻测量表明,沉积在铁和不锈钢基底上MgB2带材的超导零电阻转变温度分别为37.5K和31K,超导转变宽度分别为0.3K和1K.磁测量表明,(5K,OT)时不锈钢基底上带材的临界电流密度为6×105(A/cm2).X射线衍射谱和扫描电子显微镜图象表明样品结晶良好,晶粒生长致密.本工艺制备MgB2带材时不受系统真空度的限制,生长迅速,成本低廉,并且可以根据不同的需要任意选择基底的形状和大小.     

一个在水稻胚胎中差异表达基因的分离鉴定

通过筛选水稻开花后48～50h的原胚和120～122h的分化胚的cDNA文库,得到一个在胚胎发育过程中表达有差异的克隆,命名为OsEES,测序结果显示OsEES含有一个预测的亚精氨合成酶结构域,编码一个大小约38×103(pI6.5)的蛋白.同时RNA原位杂交的结果显示开花48～50h的原胚中的信号强度明显大于开花120～122h的分化胚,表明OsEES可能在水稻胚胎发生过程中起到一定的调控作用.     

Bio-regeneration of p-complexation desulfurization adsorbents

More and more stringent regulations of gasoline and diesel oil were proposed with the awareness of environmental protection. Hydrodesulfurization (HDS) is a conventional method to remove sulfur compounds for industrial purpose. The main drawbacks of this …     

Triterpenoid Constituents of Huperzia miyoshiana

Thirteen triterpenoids, including three new ones, miyoshianois A (1), B (2) and C (3), were isolated from Huperzia miyoshiana. The structures of these new compounds were established as 3-O-dihydroferuloyltohogenol (1), 16-oxo-3β,21β-dihydrox-y-serrat-14-en-24-ferulate (2) and 16-oxo-3a, 21β-dihydroxy-serrat-14-en-24-ferulate (3), respectively, on the basis of their spectroscopic analysis.     

Synthesis,X-Ray Structure and Characterization of a Triruthenium Cluster Complex Ru_3~Ⅲ(μ_3-O)(μ-CH_3COO)_6(py)_2Cl with Four Steps One-electron Redox Processes

Great attention is currently paid to the synthesis of polynuclear transition metal complexes as well as their photochemical, photophysical, and electrochemical properties. The design of multicomponent systems capable of performing useful light- and/or redox-induced function is of special interest1. The oxo-centered carboxylate-bridge trinuclear ruthenium clusters have been investigated extensively during recent decades because they have remarkable electron-transfer properties, intense visibl…