基于钒氧多酸与大环铜配合物构筑的三维配位聚合物的合成与表征(英文)

通过[CuL](ClO4)2(L=5,12-二甲基-1,8-二乙醇基-1,3,6,8,10,13-六氮杂环十四烷)与NH4VO3反应,得到一个钒氧多酸桥联大环铜配合物的三维配位聚合物{[CuL][VO3]2·0.67H2O}n。并对其进行了元素分析、红外光谱、紫外光谱、热重和X-射线单晶衍射测定。单晶结构测试结果表明配合物属于三方晶系,R3空间群。在晶体结构中,铜原子与大环配体上的4个氮原子和钒氧四面体[VO4]中的2个氧原子配位,形成畸变的八面体构型。钒氧多酸阴离子[V6O18]6-桥联大环配合物[CuL]2+形成一个具有一维通道的三维配位聚合物。     

两个含吡啶取代苯酚配体的铜配合物的合成与晶体结构

以2-[N,N-二(2-吡啶甲基)氨甲基]-6-醛基-4-甲基苯酚(L)为配体,合成了2个单核铜配合物[CuL(CH₃CN)(ClO₄)]ClO₄(1)和cis-[CuL(NCS)₂]·0.5C₄H₈O₂(2),对它们进行了紫外、红外、质谱、元素分析和单晶结构表征。2个配合物都属于单斜晶系,每个铜均为扭曲的八面体构型。作为四齿配体,L通过2个吡啶氮原子,1个叔胺氮原子和1个酚氧原子和铜离子配位。在配合物1中,乙腈和1个ClO₄参与配位,而在配合物2中2个硫氰根离子为顺式配位。     

吡啶取代苯酚配体构建的三个配合物的晶体结构

以2-（N，N-二（2-吡啶甲基）氨甲基）-6-醛基-4-甲基苯酚（HL）为配体合成了一个新的双核钙配合物[Ca₂L₂（NO₃）₂]（1）和一个单核镉配合物[Cd（HL）（NO₃）₂]（2），在碱性条件下，2能转化为双核镉配合物[Cd₂L₂（NO₃）₂]·H₂O（3）。分别对它们进行了红外、质谱、元素分析和单晶结构表征。配合物1和3属于单斜晶系，空间群分别为P2₁/c和C2/c，配合物2属于三斜晶系，空间群为P1。单晶结构表明，配合物1含有一个酚氧桥连的双核钙单元[Ca₂O₂]，每个钙均为八配位的扭曲十二面体构型[CaN₃O₅]，配位原子分别来自一个配体L^-的3个氮原子和一个酚氧原子、另一个配体L^-的一个酚氧原子和一个醛氧原子以及一个硝酸根的2个氧原子。2是一个单核镉配合物，八配位镉的配位构型是扭曲的十二面体[CdN₃O₅]，配位原子分别来自配体HL的3个氮原子和一个酚氧原子以及2个硝酸根的4个氧原子，醛基不参与配位。配合物3含有一个酚氧桥连的双核镉单元[Cd₂O₂]，每个镉均为七配位的单帽三棱柱构型[CdN₃O₄]，配位原子分别来自一个配体L^-的3个氮原子和一个酚氧原子、另一个配体L^-的一个酚氧原子和一个醛氧原子以及一个硝酸根的一个氧原子。     

喹啉和吡啶取代三芳基三唑的两个铜配合物的合成与晶体结构

分别以3-（2-吡啶基）-4-（4-甲基苯基）-5-（2-喹啉基）-1，2，4-三氮唑（L¹）和3-（2-吡啶基）-4-（4-氟苯基）-5-（2-喹啉基）-1，2，4-三氮唑（L²）作为配体，合成了2个新的单核铜配合物：trans-[Cu（L¹）₂（NO₃）（H₂O）]NO₃·H₂O（1）和trans-[Cu（L²）₂（NO₃）（H₂O）]NO₃·H₂O（2），对其进行了红外、元素分析和单晶结构表征。2个配合物都属于三斜晶系，P1空间群。单晶结构表明，配合物1和2中的铜离子均处于一个扭曲的八面体配位环境[CuN₄O₂]，轴向上各有一个水分子和一个硝酸根配位。配体的吡啶氮原子和三氮唑的一个氮原子参与配位，而喹啉的氮原子不配位。配合物晶体中存在O-H…O、C-H…O、C-H…N氢键和C-H…π相互作用，从而连接单核配合物形成三维网络。     

铕与2，4-二氯苯甲酸一维链状配位聚合物的合成，晶体结构和发光性质

溶液法合成了一个新的铕配位聚合物[Eu(2,4-DClBA)₃(CH₃CH₂OH)₂]_n(2,4-DClBA=2,4-二氯苯甲酸根),并用X-射线单晶衍射分析确定了其晶体结构。配合物晶体属于三斜晶系,P1空间群。标题配合物是无限一维链状聚合物,中心Eu³⁺离子通过桥联双齿2,4-二氯苯甲酸根氧原子连接。Eu³⁺离子的配位数为8     

呋喃取代三芳基三唑的单核铜配合物中共存两个不同的铜离子

分别以3-（2-吡啶基）-4-苯基-5-（2-呋喃基）-1，2，4-三氮唑（L¹）和3-（2-吡啶基）-4-（对氟苯基）-5-（2-呋喃基）-1，2，4-三氮唑（L²）作为配体，合成了2个新的单核铜配合物：trans-[Cu （L¹）₂（NO₃）₂]_0.5[Cu （L¹）₂（H₂O）₂]_0.5（NO₃）（1）和trans-[Cu （L²）₂（NO₃）₂]_0.5[Cu （L²）₂（H₂O）₂]_0.5（NO₃）·₂CH₃OH （2）。对它们进行了红外、元素分析、热重分析、单晶结构和粉末X射线衍射表征。2个配合物都属于三斜晶系，P1空间群。单晶结构表明，配合物1和2中均有2个不同的铜离子，且都处于一个扭曲的八面体[CuN₄O₂]配位环境，但在轴向上一个铜离子与2个水分子配位，另一个铜离子则与2个硝酸根配位。配体的吡啶氮原子和三氮唑的一个氮原子参与配位，而呋喃的氧原子不配位。配合物晶体中存在C—H…N、C—H…O、O—H…O氢键和C—H…π相互作用，从而连接单核配合物形成二维层状结构。     

芳酰腙和麦芽酚混合配体钒(Ⅴ)配合物的合成、表征、晶体结构及其类胰岛素活性

制备了2个钒配合物[VOLL¹] (1)和[VOLL²] (2),其中L为N'-(3,5-二溴-2-羟基苯甲基)-3-甲基苯甲酰肼,L¹为甲基麦芽酚,L²为乙基麦芽酚。通过物理化学方法和单晶X-射线衍射对配合物的结构进行了表征。在每个配合物中,钒原子都是由来自配体L中的3个配位原子,来自L¹或L²中的2个配位原子,以及1个氧基配体进行配位的,形成八面体配位构型。将配合物通过灌胃对正常的大鼠和四氧嘧啶糖尿病大鼠给药2周时间,结果表明这2个配合物在剂量为10.0和20.0 mgV·kg^-1时可以显著降低四氧嘧啶糖尿病大鼠的血糖值,而正常大鼠的血糖值却没有改变。     

喹啉-8-甲醛缩4-甲基氨基硫脲Ni(Ⅱ)/Zn(Ⅱ)/Cd(Ⅱ)/Cu(Ⅱ)配合物的合成、结构和DNA结合性质

合成并通过单晶衍射、元素分析、红外光谱表征了配合物[NiL₂]·2CH₃OH（1）,[ZnL₂]·CH₃OH（2）,[CdL₂]·CH₃CH₂OH（3）和[Cu₂L₂Cl₂]（4）（HL为喹啉-8-甲醛缩4-甲基氨基硫脲）。单晶衍射结果表明,配合物1~3结构相似,中心金属离子与来自2个硫醇化脱质子配体L^-的4个N原子和2个S原子配位,采取扭曲的八面体配位构型。而配合物4中Cu（Ⅱ）离子与1个中性配体HL和3个氯离子配位,其中2个氯离子为μ²桥联。荧光光谱结果表明,所有配合物,尤其是4与DNA的相互作用能力明显强于配体。     

噻吩和吡啶取代三芳基三唑的两个铜配合物的合成与晶体结构

分别以3-（2-吡啶基）-4-苯基-5-（2-噻吩基）-1,2,4-三氮唑（L¹）和3-（2-吡啶基）-4-（4-氯苯基）-5-（2-噻吩基）-1,2,4-三氮唑（L²）作为配体,合成了2个新的单核铜配合物：trans-[Cu （L¹）₂（MeOH）₂]（ClO₄）₂（1）和trans-[Cu （L²）₂（ClO₄）₂]·2MeCN （2）,并对其进行了红外、元素分析、单晶结构和粉末X射线衍射表征。2个配合物都属于单斜晶系,P2₁/c空间群。单晶结构分析表明,配合物1和2中的铜离子均处于一个扭曲的八面体配位环境[CuN₄O₂],其中1的轴向由2个甲醇分子配位,而2的轴向由2个高氯酸根配位。处于赤道面的配体的吡啶N原子和三氮唑的一个N原子采用螯合双齿模式参与配位,而噻吩不配位。配合物2含2个乙腈客体分子,乙腈与三氮唑环之间存在π…π堆积作用。配合物1和2中存在O-H…O、C-H…O、C-H…N氢键和C-H…π相互作用,从而连接单核配合物形成三维网络。     

叔丁基亚胺四氯合钽(V)阴离子配合物[IPrH]+[tBuN=TaCl4(py)]-的合成与表征

[^tBuN=TaCl₃(py)₂]和氮杂环卡宾(IPr =1,3-bis(2,6-diisoproylphenyl)imidazol-2-ylidene)的反应得到预料之外的叔丁基亚胺四氯合钽(V)离子配合物[IPrH]⁺[^tBuN=TaCl₄(py)]- (1)。利用核磁共振波谱,红外吸收光谱,荧光光谱,元素分析和X-Ray单晶衍射对配合物1的结构进行了表征。X-射线单晶衍射分析表明,Ta(V)中心与4四个氯和2个分别来自亚胺和吡啶配体的氮原子以八面体构型配位。     

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.     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

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.     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.