以5-甲基-3-吡唑甲酸为配体的钴(Ⅱ)、镍(Ⅱ)配合物的合成、晶体结构和性质

以5-甲基-3-吡唑甲酸（H₂MPCA）为主配体,桥联配体4,4＇-联吡啶（4,4＇-bpy）和吡嗪（pyz）为辅助配体,合成了2个新的配合物{[Co（HMPCA）₂（4,4＇-bpy）]₂·5H₂O}_n（1）和{[Ni（HMPCA）₂（pyz）]·5H₂O}_n（2）,并用元素分析、红外光谱、X射线单晶衍射结构分析、热重分析等对其进行了表征。配合物1属于正交晶系,空间群为Pccn,配合物2属于单斜晶系,空间群为P2/c。在1和2中,金属离子都位于一个扭曲的八面体配位环境中,分别由4,4＇-联吡啶（1）和吡嗪（2）两端的氮原子桥联2个相邻的金属离子,形成一维链状聚合物。考察了配合物1和2的热稳定性、荧光性能和磁性。     

以5-甲基-3-吡唑甲酸为配体的钴(Ⅱ)、镍(Ⅱ)配合物的合成、晶体结构和性质

以5-甲基-3-吡唑甲酸(H₂MPCA)为主配体,桥联配体4,4’-联吡啶(4,4’-bpy)和吡嗪(pyz)为辅助配体,合成了2个新的配合物{[Co(HMPCA)₂(4,4’-bpy)]₂·5H₂O}_n(1)和{[Ni(HMPCA)₂(pyz)]·5H₂O}_n(2),并用元素分析、红外光谱、X射线单晶衍射结构分析、热重分析等对其进行了表征。配合物1属于正交晶系,空间群为Pccn,配合物2属于单斜晶系,空间群为P2/c。在1和2中,金属离子都位于一个扭曲的八面体配位环境中,分别由4,4’-联吡啶(1)和吡嗪(2)两端的氮原子桥联2个相邻的金属离子,形成一维链状聚合物。考察了配合物1和2的热稳定性、荧光性能和磁性。     

ELECTRON-DONOR PROPERTIES OF SULFUR COMPOUNDS WITH A FEW DONOR SITES

Abstract

The structure and the coordination properties of sulfur compounds such as RS-(CH₂)n-SR, (I), n=1-10 and RS-(CH₂)nCOOR' (II), n=1,2 have been investigated by dipole moment, calorimetrie, IR-spectroscopy and cryoscopy methods.     

STUDIES ON PYRAZINE DERIVATIVES. XL. SYNTHESIS,REACTIVITY, AND TUBERCULOSTATIC ACTIVITY OF 4-HYDROXYALKYL-5-PYRAZINYL4H-[1,2,4]-TRIAZOLE-3-THIONES

2,2′-Sulfinyl-bis(4-methyl phenol) 3 and it's thio derivative have been synthesized in this work. The reduction process of sulfoxide 3 to its thio derivative 5 was accomplished in the presence of Zn/AcOH/SiO₂, under microwave irradiation. The structures have been confirmed by spectroscopic (IR, ¹HNMR, ¹³CNMR) and single crystal x-ray diffraction methods. 2,2′-Sulfinyl-bis(4-methyl phenol) 3 crystallizes in the space group Cc of the monoclinic system with four molecules in the unit cell of dimensions a = 11.425(2) Å, b = 13.530(2) Å, c = 9.5215(17) Å, β = 117.289(4) Å, and 2,2′-thio-bis(4-methyl phenol) 5 crystallizes in the space group P 2₁2₁2₁ of the orthorhombic system with four molecules in the unit cell of dimensions a = 9.021(1) Å, b = 10.523(2) Å, c = 13.607(2) Å, α = 90. The structures have been refined to final values for the crystallographic R factor of 0.0189(3) and 0.0248(5) based on 2999 and 3720 observed independent reflections respectively.     

铜三氟柳配合物的合成,结构和仿生催化溴化

合成了一系列2-羟基-4-三氟甲基苯甲酸（h₂tba）-铜配合物：[Cu（htba）₂（pz）₂] （1）,[Cu（htba）（2,2''-bipy）]（htba） （2）和[Cu（htba）₂（4,4''-bipy）] （3）（h₂tba=2-羟基-4-三氟甲基苯甲酸,pz=吡唑,2,2''-bipy=2,2''-联吡啶,4,4''-bipy=4,4''-联吡啶）,并且通过元素分析、红外光谱、紫外光谱、粉末X射线衍射、单晶X射线衍射和热重分析方法对配合物结构进行了表征。这些配合物能够在过氧化氢和溴化物存在的条件下催化苯酚红溴化,并且展示出了较高的催化溴化活性。     

铜三氟柳配合物的合成,结构和仿生催化溴化

合成了一系列2-羟基-4-三氟甲基苯甲酸（h₂tba）-铜配合物：[Cu（htba）₂（pz）₂]（1）,[Cu（htba）（2,2''-bipy）]（htba）（2）和[Cu（htba）₂（4,4''-bipy）]（3）（h₂tba=2-羟基-4-三氟甲基苯甲酸,pz=吡唑,2,2''-bipy=2,2''-联吡啶,4,4''-bipy=4,4''-联吡啶）,并且通过元素分析、红外光谱、紫外光谱、粉末X射线衍射、单晶X射线衍射和热重分析方法对配合物结构进行了表征。这些配合物能够在过氧化氢和溴化物存在的条件下催化苯酚红溴化,并且展示出了较高的催化溴化活性。     

2,6-二(1-咪唑基)萘和二羧酸构筑的金属-有机框架化合物:合成、晶体结构和荧光识别性能

利用2，6-二（1-咪唑基）萘（L）和二羧酸配体与过渡金属盐反应，通过溶剂热法合成了3个新颖的金属有机框架化合物（MOFs）：[Co（L）（AIP）]·2DMF（1），[Co（L）（AIP）]·DMF（2）和[Co（L）（IDC）（H₂O）₂]·0.5L·H₂O（3）（H₂AIP=5-氨基间苯二甲酸，H₂IDC=4，4''-亚氨基二苯甲酸）。利用元素分析、红外、X射线单晶和粉末衍射、热重分析等对MOFs进行了表征。单晶结构解析结果表明：1属于单斜晶系C2/c空间群，2和3属于三斜晶系P1空间群。1和3均为一维的链状结构，2为二维的层状结构，三者通过氢键作用形成三维超分子结构。此外，对MOFs的热稳定性和荧光性质进行了研究，发现3通过荧光猝灭对丙酮分子具有识别作用。     

含有席夫碱配体的钌配合物的合成、表征及抗肿瘤活性

设计并合成了3个含有席夫碱基团的配体（BLⁿ,n=1~3）及相应的双核联吡啶钌配合物[Ru （BLⁿ）（bpy）₂]₂（ClO₄）₄,其中bpy=2,2''-联吡啶,BLⁿ=（（PyCHN）-Ph-O-C₆H₄）₂R （PyCHN=N-2-吡啶亚甲基,R=none （Ru1）,—C （CH₃）₂（Ru2）,—SO₂（Ru3））。通过元素分析、核磁氢谱、红外光谱、质谱等方法对配体和配合物进行了表征。通过体外细胞毒性实验研究了Ru1~Ru3对宫颈癌细胞（Hela）、胃癌细胞（BGC823）、胃癌细胞（SGC-7901）三种肿瘤细胞和人正常胚肺成纤维细胞MRC-5的细胞毒性,实验结果表明Ru3的抗肿瘤活性最好,而Ru1~Ru3均对BGC823具有选择性。     

2-氯-4-氟苯甲酸与5，5'-二甲基-2，2'-联吡啶镧系配合物的晶体结构、光谱和热行为

合成并表征了2个双核配合物[Pr （2-Cl-4-FBA）₃（5,5''-DM-2,2''-bipy）]₂（1）和[Dy （2-Cl-4-FBA）₃（5,5''-DM-2,2''-bipy）]₂·2（2-Cl-4-FHBA）（2）,其中2-Cl-4-FHBA=2-氯-4-氟苯甲酸,5,5''-DM-2,2''-bipy=5,5''-二甲基-2,2''-联吡啶。配合物1以八配位的Pr³⁺为中心,其周围的配位环境为扭曲的三角十二面体。配合物2的结构是独特的,它包含2个自由的2-氯-4-氟苯甲酸分子,并以九配位的Dy³⁺为中心与周围的氮、氧原子形成扭曲的三棱镜几何构型。这2个配合物均结晶于三斜晶系P1空间群,并通过氢键相互作用和π-π堆积作用形成了一维和二维超分子结构。研究了配合物的热分解过程,结果表明配合物1和2分别分为4步和5步进行分解。同时对配合物的三维红外堆积图进行了研究,结果表明,整个热分解过程中释放出的主要气态产物是水、二氧化碳和有机小分子碎片。配合物2的荧光性质研究表明,它可以发射出Dy³⁺的特征跃迁对应的荧光。     

Synthesis of 2, 5, 5-Trimethylhepta-2, 6-Dien-4-One (Artemisia Ketone): II. Using A Thioacetal Monoxide

The polymer-bound catalyst 3a-e inserted some spacer ([-NHCO(CH_{2 10- n}; n = 0,1,2,3,4) connecting the catalytic moiety [cyclo(-(S)-Phe-(S)-His)], [(S,S)-1] and 2% cross-linked Merrifield's polymer, have been prepared and their catalytic efficiency for the enantioselective hydrocyanation of 3-phenoxybenzaldehyde was studied.     

Complex Formation of Monomeric Phosphorus Oxoacids with Sodium Ion in Donnan Exclusion Chromatography

Abstract

A method for evaluation of stability constants of very unstable and labile complexes has been proposed by the use of Donnan exclusion chromatography. The stability constants of sodium complexes of monomeric phosphorus oxoacids have been evaluated to be log β₁ = -0.04 for phosphinate, log β₁ = 0.86 and log β₂ = 0.24 for hydrogen orthophosphate and log β₁ = 0.61 and log β₂ = 0.16 for phosphonate, respectively, at I = 1.00 (CH₃)₄NCl, t = 25.0° ± 0.1°C.     

Spectrophotometric Investigation of Iron(III)-N-Phenylcin-namohydroxamic Acid System

Abstract

N-Phenylcinnamohydroxamic acid, PCHA, was found to react with iron (III) to form complex species of different colour depending upon the reaction environment. The reaction conditions for the formation of the complex species were studied in aqueous-ethanolic medium. The general spectral properties of the species were investigated. The absorption curves were found to have two isobestic points. The number and composition of the complexes were determined and found to have composition 1:1, 1:2, 1:3 (Fe: PCHA). The wavelengths of the maximum absorbances were figured out to be 535, 495, and 445 nm for the I, II, and III complex species, respectively. It was verified that the Beer's law holds for these complexes at all wavelengths, and for the mixtures at the wavelengths of the isobestic points in a wide range of pH. The stepwise stability constants have been determined by the method of isobestic point and found to be log K₁ = 11.55, log K₂ = 10.11, and log Kg₃ = 7.44 for the I, II, and III complex species, respectively. The distribution diagrams (nomograms) of the complex species as a function of pH were constructed and the molar extinction coefficients of the three consecutive complexes have also been determined.     

Differential Pulse Voltammetric Study of Complexes of Rare Earth Ion(Eu3+) with Glutarate and 1,2-Diminopropane

Abstract

The mixed complexes of Eu (III) with glutarate (Gluta) and 1,2-diaminopropane (DMPA) have been studied at 25°C, μ=0.12(NaClO₄) by differential pulse voltammetry(DPV). The reduction process in each case appears to be quasi-reversible and diffusion-controlled. The stability constants have been measured by Schaap and McMasters′ method. The stability constants of three mixed complexes formed are logβ₁₁=7. 414 for [Eu(Gluta) (DMPA)]⁺, logβ₂₁ = 8. 506 for [Eu(Gluta)₂ (DMPA)]^? and logβ₁₂ = 9. 984 for [Eu(Gluta) (DMPA)₂]⁺.     

Hydrothermal Synthesis,Crystal Structures and Magnetic Properties of two Bimetallic Cage Cluster Vanadate Complexes [Co(phen)2]2V4O12 and [Co(2,2′-bipy)2]2V4O12

Two new bimetallic cluster complexes, [Co(phen)₂]₂V₄O₁₂ 1 (phen = phenanthroline) and [Co(2,2'-bipy)₂]₂V₄O₁₂ 2 (2,2'-bipy = 2,2'-bipyridine), have been synthesized hydrothermally. X-ray crystallography reveals that both 1 and 2 possess a similar metal cage cluster core, Co₂V₄O₁₂. Magnetic studies of 1 and 2 indicate that both the complexes exhibit antiferromagnetic interactions between the cobalt(II) ions.     

Structural and solution studies of new cadmium(II) complexes with 2,2′-diamino-4,4′-bithiazole

Two new Cd(II) complexes, [Cd(DABT)(CH₃COO)₂] (1) and [Cd(DABT)(NO₃)₂] (2), DABT = 2,2′-diamino-4,4′-bithiazole, have been synthesized and characterized by single crystal X-ray crystallography. In 1, each cadmium is chelated by two nitrogens of one DABT and four oxygens of acetate, whereas 2 is a dinuclear complex and there are two Cd's with eight and six coordination: Cd₁O₆N₂ and Cd₂O₄N₂ units. The counter ion effect of the complex formation reaction between cadmium(II) nitrate and acetate with DABT has been studied by spectroscopy. The formation constants of the 1 : 1 and 1 : 2 (metal ion to ligand) complexes were evaluated by computer fitting of the absorbance–mole ratio data.     

THE INTERACTION OF 2-AMINO-2-HYDROXYMETHYL-1,3-PROPANEDIOL WITH COBALT(II) AND MANGANESE(II) IONS

Abstract

The stepwise complex formation between 2-amino-2-hydroxymethyl-1,3-propanediol (TRIS) with Co(II) and Mn(II) was studied by potentiometry at constant ionic strength 2.0 M (NaClO₄) and T = (25.0 ± 0.1)°C, from pH measurements. Data of average ligand number (Bjerrum's function) were obtained from such measurements followed by integration to obtain Leden's function, F ₀(L). Graphical treatment and matrix solution of simultaneous equations have shown two overall stability constants of mononuclear stepwise complexes for the Mn(II)/TRIS system (β₁ = (5.04 ± 0.02) M^?1 and β₂ = (5.4 ± 0.5) M^?2) and three for the Co(II)/TRIS system (β₁ = (1.67 ± 0.02) × 10² M^?1, β₂ = (7.01 ± 0.05) × 10³ M^?2 and β₃ = (2.4 ± 0.4) × 10⁴ M^?3). Slow spontaneous oxidation of Co(II) solutions by dissolved oxygen, accelerated by S(IV), occurs in a buffer solution TRIS/HTRIS⁺ 0.010/0.030 M, with a synergistic effect of Mn(II).     

Synthesis,Structure and Properties of N-(Thio)Phosphoryl Thiómides

Abstract

The analysis of all known synthesis methods of N-(thio)phosphorylthiómides of the common formula RC(S)NHP(X)R'₂ (1), where R=Alk, Ar; R'=óIk, ór, SAIk, SAr. Alk, Ar; X=O,S has been gave in this report. We worked out the simple and convenient syntheses methods of this class compounds.     

OXYDATION ALCALINE PAR L'ACIDE PERPROPIONIQUE D'ARYL MÉTHYL SULFURES EN SULFOXYDES. ETUDES EXPÉRIMENTALES ET THÉORIQUES DE L'OXYDATION NUCLÉOPHILE DE DÉRIVÉS P-SUBSTITUÉS DU THIOANISOLE PAR L'ANION PERPROPIONATE EN MILIEU MICELLAIRE

L'action de l'acide perpropionique CH₃CH₂CO₃H (1) a été étudiée en milieu alcalin micellaire (pH ～ 11; chlorure de cétyl triméthyl ammonium, CTACl) sur le thioanisole (4) et sur ses dérivés p-substitués, le p-méthoxy (2), le p-méthyl (3), le p-bromo (5) et le p-nitro (6). L'oxydation conduit exclusivement aux dérivés sulfoxydes (2a–6a). Les effets du pH, de la substitution et de la température ont permis de mieux comprendre la réaction d'oxydation de ces sulfures en sulfoxydes par l'acide perpropionique. Des calculs ab initio ont montré la cohérence de nos hypothèses. Enfin l'influence du milieu sur la cinétique de la réaction a été évalué en phase aqueuse (pH ～ 11) en présence de CTACl.

The reaction of perpropionic acid CH₃CH₂CO₃H (1) with thioanisole (4) and p-substituted thioanisoles [p-methoxy (2), p-methyl (3), p-bromo (5), and p-nitro (6)] in stoechiometric proportion has been carried out in micellar medium (cetyl trimethyl ammonium chloride, CTACl). Studies of the influence of the pH, the temperature and the substitution of the thioanisole, provide a better understanding of the sulfoxides (2a–6a) formation. Ab initio calculations have been achieved and the oxidation reaction has been studied in detail in aqueous medium (pH = 11).     

pH-dependent assembly of two polyoxometalate-based coordination polymers: structures and electrocatalytic properties

Two new polyoxometalate-based coordination polymers have been synthesized at different pHs under identical hydrothermal conditions, (Hbib)[Cu₂(bib)₂(PMo₁₂O₄₀)] (1) and (Hbib)₂[Cu(bib) (PMo₁₂O₄₀)]·2H₂O (2) (bib = 4-bis(imidazol-1-yl) benzene). Their structures were determined by single crystal X-ray diffraction analyses and characterized by routine methods. When the pH was adjusted to 2.0???2.5, 1 was obtained, which exhibits a 1-D rail-like chain. Compound 2 was obtained at pH of 2.5???3.2 and exhibits a 2-D layer with (4⁴) sql net. The pH of the reaction plays a key role in the assembly of the polyoxometalate-based coordination polymer. The electrochemical experiments indicate that 2-based carbon paste electrode possesses high catalytic efficiency and high stability towards reduction of iodate and oxidation of ascorbic acid.     

有机锡1,1′-亚甲基双(1H-吡唑-4-甲酸酯)的合成、结构与抗肿瘤活性

通过1,1′-亚甲基双(1H-吡唑-4-甲酸)(CH2(PzCO2H)2)与R3SnOH或(R3Sn)2O的反应,合成了4个有机锡1,1′-亚甲基双(1H-吡唑-4-甲酸酯)衍生物(CH2(PzCO2SnR3)2,R=Ph(1),环己基(2),Et(3),n-Bu(4))。通过红外和核磁对这些配合物进行了详细的结构表征。配合物1和3的X射线单晶衍射分析表明,这2个配合物中的吡唑氮原子均没有参与配位,但它们的羧酸根却表现出明显不同的配位方式。配合物1中羧酸根为单齿配体,且该配合物表现为简单双核结构;配合物3中羧酸根为双齿配体,其通过羧基的桥式双齿配位方式形成具有32元大环结构单元的二维配位高分子。初步的生物活性测试表明,这些有机锡衍生物对MCF-7和A549细胞具有很好的体外细胞毒性。