玫瑰花状氢氧化钴的结构和浸润性研究

在没有任何表面活性剂条件下,通过简单的方法首次合成了玫瑰花状β-Co(OH)₂微晶。玫瑰花状β-Co(OH)₂微晶宽3~5 μm,厚2~3 μm,是由平均厚度为15 nm的纳米片所组成。玫瑰花状β-Co(OH)₂组成的薄膜的接触角为158.5°±1.2°,表面处于任意的角度,水滴都不会滴落。     

两种含有十二元环的层状稀土硫酸盐的合成、结构表征及性质研究

通过溶剂热合成技术,我们得到了两种新的二维层状稀土硫酸盐：[Tb₂(SO₄)₅][(CH₃)₂NH₂]₄(1)和[Y₂(SO₄)₅][(CH₃)₂NH₂]₄(2),并通过X-射线衍射、元素分析及红外、热重对化合物进行了表征。两种化合物都属于三斜晶系,P1空间群。其中化合物1：a=0.988 7(3) nm,b=1.106 1(3) nm,c=1.535 4(4) nm,α=70.45(4)°,β=75.12(3)°,γ=67.11(3)°,Z=2;化合物2：a=0.981 6(5) nm,b=1.100 1(5) nm,c=1.528 6(8) nm,α=70.44(6)°,β=75.45(6)°,γ=67.48(6)°,Z=2。通过对晶体结构进行表征我们发现两种化合物都含有二维层状无机骨架结构,该层由2种不同类型的双链和十二元环构成。我们还对化合物1的荧光性质进行了研究,其在369 nm的激发波长下表现出了Tb³⁺的特征发射。     

两种含有十二元环的层状稀土硫酸盐的合成、结构表征及性质研究

通过溶剂热合成技术,我们得到了两种新的二维层状稀土硫酸盐:[Tb₂(SO₄)₅][(CH₃)₂NH₂]₄(1)和[Y₂(SO₄)₅][(CH₃)₂NH₂]₄(2),并通过X-射线衍射、元素分析及红外、热重对化合物进行了表征。两种化合物都属于三斜晶系,P1空间群。其中化合物1:a=0.9887(3)nm,b=1.1061(3)nm,c=1.5354(4)nm,α=70.45(0)°,β=75.12(0)°,γ=67.11(0)°,Z=2;化合物2:a=0.9816(5)nm,b=1.1001(5)nm,c=1.5286(8)nm,α=70.44(1)°,β=75.45(1)°,γ=67.48(1)°,Z=2。通过对晶体结构进行表征我们发现两种化合物都含有二维层状无机骨架结构,该层由2种不同类型的双链和十二元环构成。我们还对化合物1的荧光性质进行了研究,其在369nm的激发波长下表现出了Tb³⁺ 的特征发射。     

Kinetics of the Reactions between [(RS)2Fe(µ-S)2M(µ-S)2Fe(SR)2] n− (M = Mo, R = Ph, n = 2; M = V, R = Et, n = 3) and [Fe(SR)4]2−: Key Steps in the Assembly of Cuboidal Fe—S-based Clusters

The reaction of [S₂Mo(μ-S)₂Fe(SPh)₂]²⁻ with [Fe(SPh)₄]²⁻ produces the dicuboidal cluster [{MoFe₃S₄(SPh)₃}₂(μ-(SPh)₃]³⁻ in a three stage process studied by ¹H-n.m.r. spectroscopy and stopped-flow spectrophotometry. The initial stage involves the formation of the linear trinuclear [(PhS)₂Fe(μ-S)₂Mo(μ-S)₂Fe(SPh)₂]²⁻ and the kinetics indicate an equilibrium reaction (k₁^Mo = 2.5±0.3x 10² dm³ mol⁻¹ s⁻¹, k₋₁^Mo = 0.8±0.1 s⁻¹). The second stage involves the reduction of [(PhS)₂Fe(μ-S)₂Mo(μ-S)₂Fe(SPh)₂]²⁻ by [Fe(SPh)₄]²⁻ to form [(PhS)₂Fe(μ-S)₂Mo(μ-S)₂Fe(SPh)₂]³⁻ which subsequently rearranges to form the voided cuboidal [MoFe₂S₄(SPh)₃]²⁻. The kinetics of the second stage exhibits a simple first order dependence on the concentrations of both [(PhS)₂Fe(μ-S)₂Mo(μ-S)₂Fe(SPh)₂]³⁻ and [Fe(SPh)₄]²⁻ (k₂^Mo = 25 ± 2 dm³ mol⁻¹ s⁻¹). The Kinetics of the third stage have not been studied but must involve incorporation of the final Fe and formation of the dicuboidal [{MoFe₃S₄(SPh)₃}₂(μ-SPh)₃]³⁻. The kinetics of the reaction between [(EtS)₂Fe(μ-S)₂V(μ-S)₂Fe(SEt)₂]³⁻ and [Fe(SEt)₄]²⁻ to form [{VFe₃S₄(SEt)₃}₂(μ-SEt)₃]³⁻ have also been studied. An important difference between this reaction and the formation of the analogous [{MoFe₃S₄(SPh)₃}₂(μ-SPh)₃]³⁻ is that the formation of [{MoFe₃S₄(SPh)₃}₂(μ-SPh)₃]³⁻ from [(PhS)₂Fe(μ-S)₂Mo(μ-S)₂Fe(SPh)₂]²⁻ involves a change in the redox state of the cluster, whilst the formation of [{VFe₃S₄(SEt)₃}₂(μ-SEt)₃]³⁻ from [(EtS)₂Fe(μ-S)₂V(μ-S)₂Fe(SEt)₂]³⁻ requires no change in redox state. The reaction between [(EtS)₂Fe(μ-S)₂V(μ-S)₂Fe(SEt)₂]³⁻ and [Fe(SEt)₄]²⁻ involves two stages. The kinetics of the faster phase is associated with a rate law analogous to that observed for the reaction between [(PhS)₂Fe(μ-S)₂Mo(μ-S)₂ Fe(SPh)₂]²⁻ with [Fe(SPh)₄]²⁻: a first order dependence on the concentrations of [(EtS)₂Fe(μ-S)₂V(μ-S)₂Fe(SEt)₂]³⁻ and [Fe(SEt)₄]²⁻ (k₂^V = 1.1±0.1 x 10³ dm³ mol⁻¹ s⁻¹. This observation indicates that whilst there is no change in redox state between [(EtS)₂Fe(μ-S)₂V(μ-S)₂Fe(SEt)₂]³⁻ and [{VFe₃S₄(SEt)₃}₂(μ-SEt)₃]³⁻, reduction is necessary to catalyse the conversion of the linear [(EtS)₂Fe(μ-S)₂V(μ-S)₂Fe(SEt)₂]³⁻ into the voided cuboidal [VFe₂S₄(SEt)₃]³⁻. The results of the studies reported in this paper together with those on other putative reactions involved in the assembly of cuboidal clusters, have been combined to present a scheme of the mechanism of cuboidal cluster assembly. Electronic supplementary material Electronic supplementary material is available for this article at and accessible for authorised users.     

以三唑农药为配体的两个铜配合物的合成、晶体结构与抑菌活性

由三唑农药烯效唑和多效唑合成了2个铜配合物[CuL₄¹Cl₂](1)和[CuL₄²Cl₂·4H₂O](2)(L¹=uniconazole,L²=paclobutrazol)。通过元素分析、红外光谱和X-ray单晶衍射对其结构进行了表征。结构分析表明,1属三斜晶系,P1空间群,晶胞参数为a=0.8956(3)nm,b=1.3267(4)nm,c=1.4918(4)nm,α=94.828(3)°,β=97.774(3)°,γ=105.280(3)°,V=1.6808(9)nm³。2属三斜晶系,P1空间群,晶胞参数为a=1.02189(19)nm,b=1.329(3)nm,c=1.3664(3)nm,α=81.564(2)°,β=79.508(2)°,γ=79.185(2)°,V=1.7853(7)nm³。在2个配合物中,六配位的铜离子都采取扭曲的八面体配位构型,分别来自三唑配体的4个氮原子和2个氯原子配位。1和2都由分子间氢键连接成一维链结构。与相应的配体相比,1和2的抑菌活性明显增强。     

Pseudohexagonal motif of the arrangement of compex anions in the structure of [Ru(NH3)5Cl]2[Re6S8(CN)6]·3H2O

The [Ru(NH₃)₅Cl]₂[Re₆S₈(CN)₆]·3H₂O salt was obtained; its crystal structure was analyzed: a = 10.7713(9) Å, b = 13.9602(11) Å, c = 14.7956(11) Å, α = 91.961(3)°, β = 109.985(3)°, γ = 110.030(3)°, V = 1935.3(3) ų, space group P1ˉ, Z = 2, d _calc = 3.441 g/cm³. In the cluster anion, the Re-Re distances lie in the range from 2.594 Å to 2.612 Å. For two crystallographically independent complex cations, Ru-N_av is 2.105 Å, and Ru-Cl_av 2.329 Å. A pseudohexagonal motif of the structure was found. Original Russian Text Copyright ? 2008 by K. V. Yusenko, I. A. Baidina, E. A. Shusharina, and S. A. Gromilov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 49, No. 1, pp. 178–181, January–February, 2008.     

Synthesis and structure of complex compound Rh(III) of (NH4)2[Rh(NO2)3(NH3)(µ-OH)]2 composition

The crystalline structure of a new compound Rh(III) of (NH₄)₂[Rh(NO₂)₃(NH₃)(μ-OH)]₂ composition has been determined. The crystallographic characteristics are H₁₆N₁₀O₁₄Rh₂: a = 6.3963(2) Å, b = 9.3701(4) Å, c = 13.6646(5) Å, β = 102.266(1)°, V = 800.28(5) ų, Z = 2, d _calc = 2.432 g/cm³. The distance Rh...Rh in the dimer is 3.200 Å. Original Russian Text Copyright ? 2006 by S. P. Khranenko, I. A. Baidina, and S. A. Gromilov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 47, No. 2, pp. 380–384, March–April, 2006.     

6,6’-二硫二烟酸构筑的锌配位聚合物的合成、晶体结构和荧光性能

本文以6,6'-二硫二烟酸为主配体,通过水热法合成了新的配合物{[Zn(cpds)(dpa)]·H₂O}_n(1)(H₂cpds=6,6'-dithiodinicotinic acid,dpa=dipyridin-2-ylamine)。用X-射线单晶衍射分析确定了配合物为三斜晶系,P1空间群,其晶体学参数为a=0.8467(2),b=1.1674(3),c=1.2265(3)nm,α=73.605(3)°,β=78.656(3)°,γ=81.484(3)°,V=1.1347(5)nm³,D_c=1.850g·cm^-3,Z=2。结构分析表明配合物1为一维链状结构,相邻一维链之间堆积形成三维超分子网络结构。本文还研究了配合物的热稳定性和荧光性质。     

Crystal and molecular structure and properties of [Ni(4-NH2Py)2(iso-Bu2PS2)2] and [Co(4-NH2Py)(iso-Bu2PS2)2]

The interaction of the Co(iso-Bu₂PS₂)₂ chelate with 4-NH₂Py afforded a paramagnetic complex [Co(4-NH₂Py)(iso-Bu₂PS₂)₂] (μ_eff = 4.53 BM). Single crystals of [Ni(4-NH₂Py)₂(iso-Bu₂PS₂)₂] (I) and [Co(4-NH₂Py)(iso-Bu₂PS₂)₂] (II) were grown and used for X-ray diffraction investigation (X8 APEX diffractometer, MoK _α radiation). Crystals I are monoclinic with unit cell parameters a = 12.5336(5) Å, b = 9.4356(4) Å, c = 16.4095(6) Å; β = 111.351(1)°; V = 1807.4(1) ų; Z = 2, ρ = 1.223 g/cm³, space group P2₁/n. Crystals II are triclinic with unit cell parameters a = 8.7572(4) Å, b = 9.6934(6) Å, c = 18.665(1) Å; α = 79.374(2)°, β = 87.049(2)°, γ = 75.640(2)°; V = 1508.6(1) ų; Z = 2, ρ = 1.259 g/cm³; space group . The structures of I and II are formed by isolated mononuclear molecules. The coordination unit is NiN₂S₄ (octahedron) in I and CoNS₄ (tetragonal pyramid) in II. The 4-NH₂Py molecule is coordinated through the N atom of the heterocycle. Electronic spectroscopy data for II agree with the symmetry of the NS₄ polyhedron found by X-ray diffraction (XRD) analysis. The noncoordinated amine groups link the complex molecules via N-H...S hydrogen bonds. __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 46, No. 6, pp.1072–1080, November–December, 2005. Original Russian Text Copyright ? 2005 by T. E. Kokina, L. A. Glinskaya, E. A. Sankova, R. F. Klevtsova, and S. V. Larionov     

K2CdSnS4的溶剂热合成与晶体结构

利用溶剂热法合成了层状硫代锡(Ⅲ)酸镉(Ⅱ)化合物K₂CdSnS₄。单晶X-射线衍射分析结果表明,化合物属单斜晶系,C2/c空间群,a=1.1021(5)nm,b=1.1030(5)nm,c=1.5151(10)nm,α=90°,β=100.416(12)°,γ=90°,V=1.8114(17)nm³,Z=8,D_c=3.209g·cm^-3,M_r=437.60,μ=6.853mm^-1,F(000)=1600,λ=0.071073nm,R=0.1042,wR=0.2008。该化合物由类金刚烷[Cd₂Sn₂S₁₀]^8-结构单元互相连接形成层状结构。紫外-可见漫反射光谱研究表明,化合物为半导体,带隙为2.2eV。     

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.     

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.     

Copper-catalyzed multicomponent reactions of 2-iodoanilines,benzylamines, and elemental sulfur toward 2-arylbenzothiazoles

A relatively cheap copper salt-catalyzed, three-component approach providing 2-arylbenzothiazoles in good to excellent yields from readily available 2-iodoanilines, benzylamines, and sulfur powder is reported. This methodology allows preparation of various classes of 2-arylbenzothiazoles and provides a general, reliable approach.