FeCo2(CO)7(μ3-S)(O[P(SCH2)2]2)的合成与晶体结构

许多化学工作者对单齿膦配体（ＰＰｈ３,ＰＢｕｎ３,ＰＥｔ２Ｐｈ,Ｐ（ＯＥｔ）３,Ｐ（ＯＣ６Ｈ５）３）与母体簇合物ＦｅＣｏ２（ＣＯ）９（μ３－Ｓ）的取代反应进行过详细研究［１－３］,但对双齿膦配体与母体簇合物的取代反应研究报导较少．Ａｉｍｅ［４］合成了含双齿膦配体的簇合物ＦｅＣｏ２（ＣＯ）７（μ３－Ｓ）（Ｐｈ２ＰＣＨ２ＰＰｈ２）,并用１３ＣＮＭＲ和ＩＲ光谱方法对其结构进行了表征．到目前为止,含双齿膦配体的该类簇合物的晶体与分子结构还未见报导．ＲｏｓａｎｎａＲｏｓｓｅｔｔｉ［２］通过研究母体簇合物与…     

（四甲基二硅撑）双（3－三甲硅基环戊二烯基）－四羰基二铁的反应性

标题化合物（Ｍｅ_２ＳｉＳｉＭｅ_２）［η￣５－（３－Ｍｅ_３ＳｉＣ_５Ｈ_３）Ｆｅ（ＣＯ）_２］_２／（μ－ＣＯ）_２（Ａ）分子中的Ｆｅ－Ｆｅ键被钠汞齐还原断裂，生成相应的双铁负离子，分别与ＭｅＣＯＣｌ、ＰｈＣＯＣｌ、ＰｈＣＨ_２Ｃｌ、ＣｌＣＨ_２ＣＯＯＣ_２Ｈ_５和Ｐｈ_３ＳｎＣｌ进行亲核取代反应，生成在铁原子上引入相应取代基的产物（Ｍｅ_２ＳｉＳｉＭｅ_２）［η￣５－（３－Ｍｅ_３ＳｉＣ_５Ｈ_３）Ｆｅ（ＣＯ）_２Ｒ］_２（Ｒ：ＭｅＣＯ（１），ＰｈＣＯ（２），ＰｈＣＨ_２（３），ＣＨ_２ＣＯＯＣ_２Ｈ_５（４），Ｐｈ_３Ｓｎ（５），Ｉ（６））。Ａ在氯仿中与碘反应，得到Ｆｅ－Ｆｅ断裂的双铁碘化物，但在苯中与过量碘反应，则得到Ｆｅ－Ｉ－Ｆｅ桥联的离子型化合物（Ｍｅ_２ＳｉＳｉＭｅ_２）［η￣５－（３－Ｍｅ_３ＳｉＣ_５Ｈ_３）Ｆｅ（ＣＯ）_２］_２Ｉ·Ｉ（７）。化合物６的晶体和分子结构经Ｘ射线衍射测定，６属单斜晶系，Ｐ２１／ｃ空间群，ａ＝１．７２１７（４）ｎｍ，ｂ＝０．７７５３（２）ｎｍ，Ｃ＝１．３６２９（７）ｎｍ，β＝１０３．８０（３）°，Ｖ＝１．７６７（２）ｎｍ３，Ｚ＝４，Ｄｃ＝１．６２９９·ｃｍ－１，最终偏差因子Ｒ＝０．０５４。     

等瓣置换反应的研究——手性簇合物[η^—MeO2CC5H4）（CO）2Mo…

用Ｘ射线衍微法测定了由η＾５－ＭｅＯ２ＣＣ５Ｈ４（ＣＯ）３ＭｏＮａ和〔（η＾５－ＭｅＯ２ＣＣ５Ｈ４）（ＣＯ）２Ｗ〕Ｆｅ－（ＣＯ）３Ｃｏ（ＣＯ）３（μ３－Ｓ）的等瓣置换反应所生成的手性簇合物－〔（η＾５－ＭｅＯ２ＣＣ５Ｈ４）（ＣＯ）２Ｍｏ〕－〔（η＾５－ＭｅＯ２ＣＣ５Ｈ４）（ＣＯ）２Ｗ〕Ｆｅ（ＣＯ）３（μ３－Ｓ）的分子结构及晶体结构。晶体属Ｐ１空间群，晶胞参数ａ＝０．８７１６２（５）ｎｍ，ｂ＝０．８     

5,6—二亚甲基双环[2.2.1]庚—2—醇及其衍生物的旋光与构型

从（－）－（１Ｓ，２Ｒ，４Ｓ）－５，６－二亚甲基双环［２．２．１］庚－２－醇（Ｉ）和（－）－（１Ｓ，２Ｓ，４Ｓ）－５，６－二亚甲基双环［２．２．１］庚－２－醇（Ⅱ）出发，合成了它们的醚类和取代苯甲酸酯类光学纯的衍生物。通过［α］Ｄ测定和构型分析，发现它们是含有３个手性碳（Ｃ１，Ｃ２和Ｃ４）的桥环化合物，其旋光性与构型的关系均符合可极化度多级圆球不对称性模型。     

Eu^3＋,Bi^3＋Me2Y8（SiO4）6O2中的发光特性与取代格位

在紫外光激发下，Ｅｕ＾３＋和Ｂｉ＾３＋在Ｍｅ２Ｙ８（ＳｉＯ４）６Ｏ２基质（Ｍｅ＝Ｍｇ，Ｚｎ，Ｃａ，Ｓｒ）中分别发射红光（＾５Ｄ０－＾７Ｆ２）和蓝光（＾３Ｐ１－＾１Ｓ０）．Ｅｕ＾３＋发光的红橙比随着激发波长和Ｍｅ＾２＋的不同而变化。荧光拉曼光谱表明，Ｅｕ＾３＋在四种基质中同时占据了４ｆ格位和６ｈ格位。依据Ｂｉ＾３＋发光的Ｓｔｏｋｅｓ位移推断，当Ｍｅ＝Ｃａ，Ｚｎ时，Ｂｉ＾３＋主要占据４ｆ格位，而当Ｍｅ     

高电势铁硫蛋白的模型化合物：2,4,6—三苯基苯硫酚的4Fe4S簇合 …

新型簇合物（ｎ－Ｂｕ４Ｎ）２「Ｆｅ４Ｓ４（ｔｐｂｔ）４」（ｔｐｂｔ－２，４，６－三苯基苯硫酚基）通过２，４，６－三苯基苯硫酚和（ｎ－Ｂｕ４Ｎ）２「Ｆｅ４Ｓ４９Ｓ－ｔ－Ｂｕ０４」在ＤＭＦ中进行配体交换反应合成得到。该簇合物在ＣＨ３ＣＮ溶液中的「Ｆｅ４Ｓ４」＾３＋／２＋和「Ｆｅ４Ｓ４」＾２＋１／＋的氧化还原电位分别为－０．１４和－１．３１ＶｖｓＳＣＥ。     

（四甲基二硅撑）二（3－三甲硅基环戊二烯基）四羰基二铁及其相关化合物的合成及结构

１，２－二（三甲硅基环戊二烯基）四甲基二硅烷与Ｆｅ（ＣＯ）_５在二甲苯中于１０５～１１０℃反应除分离到少量标题化合物（Ｍｅ_２ＳｉＳｉＭｅ_２）［η－（３－Ｍｅ_３ＳｉＣ_５Ｈ_３Ｆｅ（ＣＯ）］_２（μ－ＣＯ）_２（５）外，主要是生成了脱Ｍｅ_３Ｓｉ基的产物（Ｍｅ_２ＳｉＳｉＭｅ_２）［η－Ｃ_５Ｈ_４Ｆｅ（ＣＯ）］_２（μ－ＣＯ）_２（１）及１的热重排异构体［Ｍｅ_２ＳｉＣ５Ｈ４－Ｆｅ（ＣＯ）_２］_２（２）．将５的二甲苯溶液加热回流１８ｈ，则转化为其异构体［Ｍｅ_２Ｓｉ（Ｍｅ_３ＳｉＣ_５Ｈ_３）Ｆｅ（ＣＯ）_２］_２（６）．脱硅基发生在由相应反应物制备５的过程中。且脱硅基是与反应物中（Ｍｅ_２ＳｉＳｉＭｅ_２）桥的存在有关．５的晶体结构经Ｘ射线衍射测定属单斜晶系，Ｐ２_１／ｍ空间群，晶体学数据：ａ＝０．６７８０（１）ｎｍ，ｂ＝２．２３０３（９）ｎｍ，ｃ＝０．９９８８（１）ｎｎ，；β＝９８．９６（１）°，Ｖ＝１．４９６０ｎｍ~３．Ｚ＝２，Ｄ_ｃ＝１．３６ｇ／ｃｍ~３．     

环状配合物Me_2Si［η~5－C_5H_4Fe（CO）_2］_2SnR_2的合

通过ＳｎＣｌ_２对化合物Ｍｅ_２Ｓｉ［η~５－Ｃ_５Ｈ_４Ｆｅ（ＣＯ）］_２（μ－ＣＯ）_２（Ⅰ）中Ｆｅ－Ｆｅ键的插入反应以及Ⅰ被Ｎａ－Ｈｇ齐还原所生成的相应双铁负离子｛Ｍｅ_２Ｓｉ［η~５－Ｃ_５Ｈ_４Ｆｅ（ＣＯ）_２］_２｝~（２－）与ＳｎＲ_２Ｃｌ_２（Ｒ＝Ｍｅ，Ｐｈ）的亲核反应，合成了环状化合物Ｍｅ_２Ｓｉ［η~５－Ｃ_５Ｈ_４Ｆｅ（ＣＯ）_２］_２ＳｎＲ_２［Ｒ＝Ｃｌ（１），Ｍｅ（２），Ｐｈ（３）］。以元素分析、ＩＲ和~１ＨＮＭＲ谱表征了它们的结构，并用Ｘ射线衍射测定了配合物３的晶体结构。３为单斜晶系，空间群Ｐ２_１／ｎ，ａ＝１．０３８４（３）ｎｍ，ｂ＝１．６３８４（１）ｎｍ，ｃ＝１．５７６２（５）ｎｍ，β＝９７．９３（２）°，Ｖ＝２．６５６（２）ｎｍ~３，Ｚ＝４，Ｄｘ＝１．７１ｇ／ｍＬ。     

活泼配盐[(μ-RE)(μ-E′)Fe_2(CO)_6][Et_3NH][E,E′=S,Se]的亲电反应研究——蝶状Fe_2SSe及Fe_2Se_2簇合物的合成及表征

本文由［（μｔＢｕＳ）（μＣＯ）Ｆｅ２（ＣＯ）６］［Ｅｔ３ＮＨ］和硒粉形成的［（μｔＢｕＳ）（μＳｅ）Ｆｅ２（ＣＯ）６］［Ｅｔ３ＮＨ］，分别与溴化苄，二碘甲烷及邻一、间一、对一双（溴甲基）苯反应，合成了蝶状Ｆｅ２ＳＳｅ单簇物（μｔＢｕＳ）（μＰｈＣＨ２Ｓｅ）Ｆｅ２（ＣＯ）６（３ａ）和双簇物［（μｔＢｕＳ）Ｆｅ２（ＣＯ）６］２（μＳｅＺＳｅμ）［Ｚ＝ＣＨ２，ｏ．ｍ．ｐ双（亚甲基）苯］（４ａｄ）。类似地，由［（μＰｈＳｅ）（μＣＯ）Ｆｅ２（ＣＯ）６］［Ｅｔ３ＮＨ］和硫粉或硒粉所形成的［（μＰｈＳｅ）（μＳ）Ｆｅ２（ＣＯ）６］［Ｅｔ３ＮＨ］或［（μＰｈＳｅ）（μＳｅ）Ｆｅ２（ＣＯ）６］［Ｅｔ３ＮＨ］分别与对一双（溴甲基）苯反应合成了蝶状Ｆｅ２ＳＳｅ和Ｆｅ２Ｓｅ２双簇物［（μＰｈＳｅ）Ｆｅ２（ＣＯ）６］２［μＳ（ｐＣＨ２Ｃ６Ｈ４ＣＨ２）Ｓμ］（５ａ）及［（μＰｈＳｅ）Ｆｅ２（ＣＯ）６］２［μＳｅ（ＰＣＨ２Ｃ６Ｈ４ＣＨ２）Ｓｅμ］（５ｂ）。所有产物均经元素分析、ＩＲ和１ＨＮＭＲ表征。     

手性助剂诱导下的α,β-不饱和酮的不对称加氢反应及其在合成(R)-麝香酮中的应用

在ＴＨＦ溶液中，４０－６０℃及０．３－０．５ＭＰａ氢压条件下，［ＲｕＣｌ２（ｃｈｔ）］２＋（Ｓ）－ＢＩＮＡＰ手性催化剂体系催化不饱和手性缩酮２选择加氢，再经脱去手性二醇，即可高立体选择性地制得（Ｒ）－３－甲基环十五烷酮（４，（Ｒ）－（－）－麝香酮），化学收率≥９５％，光学纯度≥９７％．手性缩酮２由Ｄ－苏糖醇或Ｄ－葡萄糖衍生的手性二醇３与３－甲基环十五烯－２－酮１生成．     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.