三核铜配合物的合成、表征及其催化性能

采用溶剂热法合成了以三核碘化亚铜（CuI）四面体结构为活性中心的硅氢加成反应催化剂,探讨了物料比对产物收率的影响。结果说明了当配体与碘化亚铜的摩尔比为1：6时,产物收率最高。通过元素分析、傅里叶红外光谱分析、X射线光电子能谱分析、X射线单晶体衍射分析、紫外可见光光谱分析、热失重分析对配合物的化学组成、空间结构及性能进行表征,并进一步通过甲基苯基乙烯基树脂和甲基苯基含氢硅油的硅氢加成反应进行催化固化效果验证。结果说明了在催化剂填加量为0.04%、固化温度为150℃的优化条件下反应24h,共混体系固化效果最佳。该配合物对硅氢加成反应具有很好的催化性能,并且原料成本低、制备方法简单、晶体颗粒方便储存,有望解决硅氢加成反应中贵金属催化剂的高成本问题。     

Synthesis,Characterization, and Antimicrobial Activity of Silver(I) and Copper(II) Complexes of Phosphate Derivatives of Pyridine And Benzimidazole

Two silver(I) complexes—{[Ag(4‐pmOpe)]NO₃}_n and [Ag(2‐bimOpe)₂]NO₃—and three copper(II) complexes—[Cu₄Cl₆O(2‐bimOpe)₄], [CuCl₂(4‐pmOpe)₂], and [CuCl₂(2‐bis(pm)Ope]—were synthesized by reaction of silver(I) nitrate or copper(II) chloride with phosphate derivatives of pyridine and benzimidazole, namely diethyl (pyridin‐4‐ylmethyl)phosphate (4‐pmOpe), 1H‐benzimidazol‐2‐ylmethyl diethyl phosphate (2‐bimOpe), and ethyl bis(pyridin‐2‐ylmethyl)phosphate (2‐bis(pm)Ope). These compounds were characterized by ¹H, ¹³C, and ³¹P NMR as well as IR spectroscopy, elemental analysis, and ESIMS spectrometry. Additionally, molecular and crystal structures of {[Ag(4‐pmOpe)]NO₃}_n and [Cu₄Cl₆O(2‐bimOpe)₄] were determined by single‐crystal X‐ray diffraction analysis. The antimicrobial profiles of synthesized complexes and free ligands against test organisms from the ATCC and clinical sources were determined. Silver(I) complexes showed good antimicrobial activities against Candida albicans strains (MIC values of ～19 μM ). [Ag(2‐bimOpe)₂]NO₃ was particularly active against Pseudomonas aeruginosa and methicillin‐resistant Staphylococcus epidermidis, with MIC values of ～5 and ～10 μM , respectively. Neither copper(II) complexes nor the free ligands inhibited the growth of test organisms at concentrations below 500 μg mL^?1.     

2-取代苯并咪唑与铜（II）配合物的微波合成与表征

采用2-取代基苯并咪唑化合物、氯化铜为原料、丙酮或2-丁酮为溶剂,在微波辐射下合成了2-苄基苯并咪唑(BIm_a)和1-(对甲氧基苄基)-2-(对甲氧基苯基)苯并咪唑(BIm_b)的铜配合物,收率分别为80%和75%.测得BIm_a和BIm_b铜配合物熔点分别为144.7～145.8 ℃和224.5～226.0℃.应用摩尔电导率、XRD、紫外光谱、SEM和热分析测试对目标配合物进行表征,摩尔电导率、紫外和红外光谱解析表明,2-取代苯并咪唑配体与Cu(Ⅱ) 发生了配合反应;XRD和SEM表征证明晶型为单斜晶系;热分析得出BIm_a、BIm_b和氯化铜的配位数分别为1和1/2.     

Synthesis,characterization and antibacterial activity of Pd(II), Pt(II) and Ag(I) complexes of 4-ethyl and 4-(p-tolyl)-1-(pyridin-2-yl)thiosemicarbazides

Pd(II), Pt(II) and Ag(I) ions were found to form stable complexes with 4-(p-tolyl)- or 4-ethyl-1-(pyridin-2-yl)thiosemicarbazides (Hp-TPTS or HEPTS). The complex structure was elucidated by analysis (elemental and thermal), spectroscopy (electronic, IR and ¹H NMR spectra) and physical measurements (magnetic susceptibility and molar conductance). The ligands coordinate to the metal ions as monobasic bidentate through nitrogen and sulfur atoms. The electronic spectra of the Pt(II) complexes in DMF showed a metal to ligand charge transfer transition at 11,935–13,260 cm^?1. The structural, electronic and vibrational features of HEPTS and Hp?TPTS were discussed on the basis of semi-empirical quantum mechanic calculations [ZINDO/S and semi-empirical parameterization (PM3)]. The simulated IR and electronic spectra are found reasonable in accordance with the experimental data. Finally, the antibacterial activities of the ligands and their complexes were investigated and some were found promising.     

Synthesis,spectral and structural study of sulfur-containing copper(II) complexes

A series of four new copper(II) complexes [Cu(H₂L)(L¹)] 1, [Cu(H₂L)(PMDT)] 2, [Cu(H₂L)(Dien)] 3 and [Cu(H₂L)(L²)] 4 have been synthesized by template condensation (H₂L=thiodiglycolic acid, L¹=N-[(1)-1-(4-methylphenyl)ethylidene]benzohydrazide, PMDT=N,N,N′,N′,N ^′′-pentamethyldiethylene- triamine, Dien=diethylenetriamine L²=N-[(1)-pyridin-2-ylmethylidene]benzohydrazide). The bonding and stereochemistry of the complexes have been characterized by molar conductance, elemental analysis, magnetic susceptibility, infrared, UV–visible, electron paramagnetic resonance structural studies and electrochemical studies. g-Values were calculated for all complexes in polycrystalline form as well as in DMSO solution. The magnetic and spectral data indicate square pyramidal geometry for 1 and octahedral geometry for 2–4 complexes. Cyclic voltammograms for all the complexes are similar and involve two irreversible redox processes. Their biological properties have also been studied. The thio complexes show more antibacterial activity than the controlled one. The antibacterial activities of the compounds have also been tested against Escherichia coli with different concentrations.     

Equilibrium and kinetic studies of the extraction of chelated copper(II) anions with Aliquat 336

The equilibrium and kinetics of solvent extraction of Cu²⁺ from aqueous solutions containing equimolar EDTA with Aliquat 336 in n‐decanol and kerosene at 298 K were investigated. The concentrations of Cu²⁺ (8–50 mol m^?3), Cl^? (5–60 mol m^?3), and Aliquat 336 (20–100 mol m^?3) were varied. A semi‐empirical model with three parameters was proposed to describe the equilibrium behavior, in which the non‐idealities in both aqueous and organic phases were considered. Over the ranges studied, the model agreed reasonably well with the experimental data (standard deviation, 15%). The forward and backward reaction rate constants were determined as (5.31 ± 0.16)×10^?6 m^9/4 mol^?3/4 s^?1 and (2.62 ± 0.09)×10^?7 s^?1, respectively, at 298 K. An interfacial reaction mechanism was proposed, which revealed that the reaction between the chelated anions and trimeric amine molecules at the interface was rate limiting. The derived rate laws were consistent with the experimental results. © 2002 Society of Chemical Industry     

Synthesis and crystal structures of copper(I) iodide complexes chelating with bis(ethylamidophosphine)

Two copper(I) iodide complexes with polydentate bis(ethylamidophosphine) ligands were synthesized, characterized with crystal structures. They include a dimeric complex [Cu(μ-I)(CH₂NHCOC₂H₄PPh₂)₂]₂ 1 containing a planar Cu₂I₂ rhombohedron with two doubly bridged ligands and a tetrameric complex {Cu₄(μ-I)₄[(CH₂NHCOC₂H₄PPh₂)₂]₂} 3 with all the coppers and iodines forming a highly distorted cubane geometry.     

含有蒽酰亚胺的铜(I)配合物的合成、结构及光谱研究

合成了两个含蒽酰亚胺基团的新配体N-(2-(6-氨基吡啶))-9-蒽酰亚胺(L1)和N,N′-(2,6-吡啶基)-二(9-蒽酰亚胺)(L2),以及L1的铜(I)配合物[CuL1(PPh3)2](BF4)(1),并研究了它们的结构和光谱性质.理论计算表明配体L1配位前为反式构象,配合物1的晶体结构显示L1配位后发生结构扭曲呈顺式构象,羰基氧原子与铜(I)离子配位.光谱研究表明配体L1和配合物1都表现出蒽的特征吸收和发射峰.     

Synthesis and characterization of copper(I) complexes from triphenylphosphine and isatin Schiff bases of semi- and thiosemicarbazide

The reaction of isatin-3-thiosemicarbazone (ITC, 1) or isatin-3-semicarbazone (ISC, 2) with nitrato bis(triphenylphosphine)copper(I) gave the four coordinate copper(I) complexes [Cu(PPh₃)₂(ITC)]NO₃ (3) and [Cu(PPh₃)₂(ISC)]NO₃ (4). The synthesized complexes were characterized by FT-IR, UV–VIS, Raman and elemental analysis. The crystal structure of 3 was investigated by single crystal X-ray diffraction. The ITC coordinates to the copper(I) ion in a bidentate fashion via the N(imine) and S atoms which along with two triphenylphosphine ligands form a tetracoordinate complex. The complex has a distorted tetrahedral coordination environment. Crystal data at 150.0 K: space group P2₁/c with a=12.5777(4), b=15.2062(5), c=21.9057(7) Å, β=95.628(3)^o, Z=4, R ₁=0.049.

     

Novel syntheses of an aliphatic series of new dithiocarboxylates and perthiocarboxylates of copper (I) and some of their complexes with triphenylphosphine

ABSTRACT

Copper(I) alkyldithiocarboxylates (1a), (1b) and (1c) of formula [RCS₂Cu]₄ [(1a) R?=?t-Bu, (1b) R?=?n-Bu, (1c) R?=?sec-Bu] and copper(I) alkylperthiocarboxylates (2a), (2b) and (2c) of formula [RCS₃Cu]₄ [(2a) R?=?t-Bu, (2b) R?=?n-Pr, (2c) R?=?cyclohexyl] were prepared from the reaction of Grignard reagents with carbon disulfide, in the presence of CuBr. Cu(I) Dithiocarboxylates (1a) and (1b) were treated with triphenylphosphine to give, respectively, complexes (3a) and (3b) of formula RCS₂Cu(PPh₃)₂ [(3a) R?=?t-Bu, (3b) R?=?n-Bu]. The compounds obtained were characterized by various spectroscopic tools including NMR (¹H, ¹³C, ³¹P) spectroscopy, and single crystal X-ray diffraction.     

Synthesis,Spectroscopy, Single-Crystal Structure Analysis and Antibacterial Activity of Two Novel Complexes of Silver(I) with Miconazole Drug

In a previous article, we reported on the higher toxicity of silver(I) complexes of miconazole [Ag(MCZ)₂NO₃ (1)] and [Ag(MCZ)₂ClO₄ (2)] in HepG2 tumor cells compared to the corresponding salts of silver, miconazole and cisplatin. Here, we present the synthesis of two silver(I) complexes of miconazole containing two new counter ions in the form of Ag(MCZ)₂X (MCZ = 1-[2-(2,4-dichlorobenzyloxy)-2-(2,4-dichlorophenyl)ethyl]-1H-imidazole]; X = BF₄⁻ (3), SbF₆⁻ (4)). The novel silver(I) complexes were characterized by elemental analysis, ¹H NMR, ¹³C NMR and infrared (IR) spectroscopy, electrospray ionization (ESI)-MS spectrometry and X-ray-crystallography. In the present study, the antimicrobial activity of all obtained silver(I) complexes of miconazole against six strains of Gram-positive bacteria, five strains of Gram-negative bacteria and yeasts was evaluated. The results were compared with those of a silver sulfadiazine drug, the corresponding silver salts and the free ligand. Silver(I) complexes exhibited significant activity against Gram-positive bacteria, which was much better than that of silver sulfadiazine and silver salts. The highest antimicrobial activity was observed for the complex containing the nitrate counter ion. All Ag(I) complexes of miconazole resulted in much better inhibition of yeast growth than silver sulfadiazine, silver salts and miconazole. Moreover, the synthesized silver(I) complexes showed good or moderate activity against Gram-negative bacteria compared to the free ligand.     

琥珀酰化壳聚糖-铜(Ⅱ)-苯并咪唑衍生物配合物的合成、表征及抗菌活性

文章利用琥珀酸酐对壳聚糖进行改性,并合成了两个新的配合物:sucts-Cu(Ⅱ)-hpb(1)和sucts-Cu(Ⅱ)-tbz(2)[sucts=琥珀酰化壳聚糖,hpb=2-(2’-吡啶)-苯并咪唑,tbz=2-(4′-噻唑基)苯并咪唑]。应用红外光谱,紫外-可见光谱,原子吸收光谱对配合物进行了表征,采用试管倍比稀释法研究了这些配合物对苏云金杆菌、枯草芽孢杆菌、大肠杆菌和金黄色葡萄球菌的抑制作用。结果表明,两种配合物对四种细菌均有较强的抑菌活性,配合物1、2,最小抑菌浓度(MIC)分别为62.5～125μg.mL-1和125～250μg.mL-1,抗菌效果明显强于自由配体。     

甲基磺酸铜催化合成柠檬酸三(2-乙基己基)酯的研究

研究了以甲基磺酸铜催化柠檬酸和2-乙基己醇的酯化反应,考察了反应温度、催化剂用量、醇酸摩尔比等对反应的影响。结果表明,甲基磺酸铜催化合成柠檬酸三(2-乙基己基)酯的最佳反应条件为:n(2-乙基己醇)∶n(柠檬酸)=1.08∶0.3,催化剂用量0.30%(以酸的物质的量计),反应温度120~130℃,负压操作。在最佳反应条件下,柠檬酸三(2-乙基己基)酯收率在98%以上;反应结束后,催化剂通过简单的相分离,即可重复使用,重复使用5次,其催化活性无明显下降,产品收率仍可达到90%以上。     

2-羟基-4-甲氧基二苯甲酮合铜(Ⅱ)配合物的合成与表征

合成了一种新的2-羟基-4-甲氧基二苯甲酮合铜(Ⅱ)配合物,并用热重、红外光谱、紫外光谱等手段进行了表征。TG分析结果表明,配合物中金属离子与配体的化学计量比为1∶2,且该配合物在220℃以下结构保持稳定,在220~550℃存在两个失重阶段,均为其热分解过程,最终分解产物为CuO。IR分析得出,配体中羰基氧、邻位羟基氧与金属离子配位。紫外光谱分析则进一步证实了上述IR结果,同时表明,配合并未改变2-羟基-4-甲氧基二苯甲酮的性质,配合物仍然具有吸收紫外线的能力。     

Synthesis, Spectral and Antibacterial Studies of Copper(II) Tetraaza Macrocyclic Complexes

A novel family of tetraaza macrocyclic Cu(II) complexes [CuLX(2)] (where L = N(4) donor macrocyclic ligands) and (X = Cl(-), NO(3) (-)) have been synthesized and characterized by elemental analysis, magnetic moments, IR, EPR, mass, electronic spectra and thermal studies. The magnetic moments and electronic spectral studies suggest square planar geometry for [Cu(DBACDT)]Cl(2) and [Cu(DBACDT)](NO(3))(2) complexes and distorted octahedral geometry to the rest of the ten complexes. The biological activity of all these complexes against gram-positive and gram-negative bacteria was compared with the activity of existing commercial antibacterial compounds like Linezolid and Cefaclor. Six complexes out of twelve were found to be most potent against both gram-positive as well as gram-negative bacteria due to the presence of thio group in the coordinated ligands.     

Control of debromination in solution polymerisation of copper(I) 4-bromobenzenethiolate

Fresh poly(phenylene sulfide) (PPS) fibers have pleated surface morphology and banded texture. These structural features are similar to those of poly(phenylene terephthalamide) fiber (Kevlar), whereas some unique morphologies were observed for the long-term stored PPS fibers, which have not been found with liquid crystalline polymer fibers including Kevlar. The long-term stored PPS fibers show a decreased T_g and a decreased onset temperature of melting, compared with their fresh counterparts, which is attributed to stress relaxation and resulting disorientation in the amorphous region of the fibers. Combination of the observed typical morphologies with polarized optical microscopy and X-ray diffraction analysis suggests that PPS possesses liquid crystalline nature.     

Synthesis, photoluminescence, and theoretical studies of novel Cu(I) complex

A novel diimine Cu(I) complex [Cu(ABPQ)(DPEphos)]BF₄ [ABPQ and DPEphos are acenaphtho[1,2-b]bipyrido[2,3-h;3,2-f]quinoxaline and bis(2-(diphenylphosphanyl)phenyl) ether, respectively] is synthesized, and its photophysical properties are experimentally and theoretically characterized. The emission bands centered at ca. 400/470 and 550 nm of [Cu(ABPQ)(DPEphos)]BF₄ are attributed to the ligand-centered π → π* transition and the metal-to-ligand charge transfer dπ(Cu) → π*(N–N) transition, respectively. The luminescence quantum yield of [Cu(ABPQ)(DPEphos)]BF₄ in CHCl₃ is found to be about five times higher than that of [Cu(Phen)(DPEphos)]BF₄.     

Synthesis and characterization of coordination polymers of Hg(II) with poly(thiooxamides)

Coordination polymers of Hg(II) with dithiooxamide, poly(ethylene thiooxamide), poly(butane thiooxamide), and poly(hexane thiooxamide) have been synthesized. All coordination polymers are solid compounds insoluble in common organic solvents. Coordination polymers have been characterized by elemental analysis, IR spectra, and thermogravimetric analysis and structures have been proposed leading to coordination of metal through S alone as well as N and S both. Thermal stability of the polymers has also been discussed.     

A rapid approach to urushiol–copper(I) coordination polymer under UV irradiation

Urushiol–metal polymers have attracted more and more attention in China because of their wide applications as a heavy anticorrosive coating in chemical industry. They could also offer many novel properties, including catalytic activity, magnetic property, semiconductive properties, flame retarding performance, etc., and significant progresses have been achieved in synthesis and study on the mechanism of these polymers. In this paper, a rapid method for fabrication of urushiol–copper(I) coordination polymer was developed under UV irradiation within 2 min. The formation and thermo-stability of the cured films were characterized by ESR, XPS, FT-IR, TGA, etc. The results suggested the coordination occurred between copper(I) ion and oxygen under UV irradiation. In the course of UV irradiation, the hydroxyl groups on the phenyl ring of urushiol were dissociated to urushiol semiquinone, and then coordinated with copper(I) ions generated by deoxidization of copper(II) ion. At the same time, crosslinking reaction on the long aliphatic unsaturated side chain occurred to form polymer. TG analysis showed that the polymer had excellent thermo-stability.     

Synthesis and characterization of dinuclear silver(I) complexes with exchangeable nitrile ligands

We have prepared three silver(I) complexes of the type [Ag₂(P ∩ N)₃(NCR)](BF₄)₂ with (R = Me, Et, Ph). The crystal structures of the complexes were determined. The nitrile ligands can be easily exchanged by re-crystallisation in the respective nitrile. The luminescence properties were also investigated.