Synthesis, Crystal Structure and Luminescent Properties of the Indium(Ⅲ) Complex Based on 2,6-Bis(1-phenylbenzimidazol-2-yl)pyridine

The complex [In（bpbp）Cl3]·H2O, where bpbp is 2,6-bis（1-phenylbenzimidazol- 2-yl）-pyridine （bpbp）, was synthesized and characterized by X-ray single-crystal structure analysis. For the complex： C31H21Cl3InN5·H2O, Mr = 702.71, monoclinic, space group, P21/n, a = 9.3918（10）, b = 21.024（2）, c = 14.5323（15）, β = 96.938（2）°, V = 2848.4（5）3, Z = 4, Dc = 1.639 g/cm3, λ = 0.71073, μ（MoKα） = 1.147 mm-1, F（000） = 1408, S = 1.00, R = 0.0430 and wR = 0.1438 for 4620 observed reflections with Ⅰ 〉 2σ（Ⅰ）. It is a neutral complex. The In（Ⅲ） ion adopts a distorted trigonal bipyramidal geometry coordinated by three nitrogen atoms of the ligand and three chlorine atoms. The complex emits blue luminescence with emission peaks at 430 nm in the solid state.

Indium (III) Tribromide : An Excellent Catalyst for Biginelli Reaction

A highly efficient catalyst indium (III) tribromide is used to synthesize 5-alkoxy-carbonyl-4-hydrocarbyl-3,4-dihydropyrimidin-2(1H)-ones by a three-component coupling of beta-keto ester, aldehydes and urea through improved Biginelli reaction.

Oxone-Mediated Oxidative Esterification of Heterocyclic Aldehydes Using Indium(III) Triflate

Recent investigations have shown the oxone-mediated oxidative methyl esterification of benzaldehyde derivatives using methanol. The reactions were accelerated in the presence of indium(III) triflate, a trivalent indium reagent, in many cases. Based on this method of methyl esterification of benzaldehyde derivatives, we further explored an application to heterocyclic aldehydes. The reactions were examined using methanol as well as other alcohols in order to establish a suitable range.

Highly-Efficient Conversion of Primary Amides to Nitriles Using Indium(III) Triflate as the Catalyst

Indium(III) triflate, a trivalent indium reagent, was shown to be a highly-efficient catalyst for the conversion of primary amides to the corresponding nitriles. The successful reactions required 5 mol% of indium(III) triflate, and toluene was proved to be the most suitable solvent. Various amides were subjected to this method, and each produced the corresponding nitriles in excellent yields.

Synthesis and Characterization of Heteropoly Complexes of Indium with Metal-centred Undecatungstate Ligands

New indium heteropoly undecatungstometalate complexes of general formula K_n In( H_2O) MW_(11)O_(39) .xH_2O (M = Cr(Ⅲ) , Fe( Ⅲ ), Co(Ⅱ) or Zn( Ⅱ) ) were prepared by the stepwise acidification and the stepwise addition of materials. The products were characterized by elemental analysis, ion-exchange, IRspectra, UV spectra, X-ray powder diffraction and thermal analysis. The results show that the structure ofthe products derives from the Keggin structure. Their themial stability is higher than that of the homolo-gous dedecatungstometalates .

Synthesis and Crystal Structure of a Novel Hexanuclear Copper-indium Thiolate Complex [(InCl)_2(OMe)(μ-OMe)_2(μ_3-OMe)(μ-SPr^n)_2(CuPPh_3)]_2

A novel hexanuclear copper-indium thiolate complex, [（InCl）2（OMe）（μ-OMe）2（μ- OMe）（μ-SPrn）2（CuPPh3）]2 1, was synthesized from the reaction of NaSPrn, InCl3 and [Cu（Me- CN）a][PF6] in the presence of Ph3P and characterized by single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P211n with a = 11.3533（8）, b = 15.4939（11）, c = 20.5189（14） A, β = 98.577（2）°, V = 3569.0（4） A3, Z = 2, C56H82Cl4Cu2In4O8P2S4, Mr = 1801.56, Dc = 1.676 g/cm3,μ（MoKa） = 2.213 mm^-1, F（000） = 1796, S = 0.985, the final R = 0.0559 and wR = 0.1099 for 8878 observed reflections with I 〉 2σ（I） and 367 variables. Complex 1 consists of two CuPPh3 fragments which symmetrically side-attach to the tetranuclear core of [InaCl4（OMe）2（μ-OMe）a（μ- OMe）2（μ-SPrn）4] by coordinating with sulfur atoms of propane-thio moieties. The average In-Ot （terminal）, In-μ-O and In-μ3-O bond distances are 2.305（4）, 2.144（4） and 2.294（4） A, respectively.

The Aggregates in LB Films of Schiff base Aluminium (III) Complex

The surface pressure-area (pi -A) isotherm of Schiff base aluminium (III), tris (2-hydroxy-5-nitro-N-dodecyl-benzylideneaminato) aluminium (III) (denoted as Al(TAl2)(3)), on pure water subphase was investigated. The molecular area, 0.48 nm(2), is one-third of expected value that indicated the aggregation took place. The Langmuir-Blodgett (LB) films of Al(TAl2), was transferred and characterized. The AFM image confirmed the formation of aggregates.

Oxone-Mediated Preparation of Ester Derivatives Using Indium(III) Triflate and Various Alcohols

Esters are known as one of the most fundamental chemical moieties and also essentially useful components, especially for medicinal agents. Herein, using benzaldehyde and its derivatives as starting materials, Oxone-mediated preparation of ester derivatives in the presence of a catalytic amount of indium(III) triflate is described. Alcohols with various chain lengths, which functioned as solvents and substrates, were examined. Overall, the oxidative esterification starting with benzaldehyde derivatives possessing electron withdrawing groups proceeded smoothly and gave sufficient yields, in comparison to the reactions with the derivatives having electron donating groups.

Dehydrosulfurization of Aromatic Thioamides to Nitriles Using Indium(III) Triflate

The efficient dehydrosulfurization of thioamides to nitriles was carried out using indium(III) triflate as a catalyst. Based on the results of the initial study, the optimal reaction conditions required 5 mol% of indium(III) triflate with toluene as the practical solvent. Various thioamides were successfully converted to nitriles in high yields.

STUDY ON BINUCLEAR COPPER(I)COMPLEXES III.SYNTHESIS,CHARACTERIZATION AND ELECTROCHEMISTRY OF DICHLORO-TRIS(4-VINYLPYRIDINE)-DICOPPER(I)COMPLEX

Recent years,many novel complexes have been prepared by using hetero-bidentate ligands.However,complexes with such ligands as 4-vinylpyridine which has two different coordinating sites have not been reported,and only a few complexes of Cu(I)have been published^(1-3).The title complex Cu_2(C_5H_4N·CH=CH_2)_3Cl was prepared and characterized by elemental analyses,ICP,IR,and electronic spectra.Its conductivity,oxidation potential and reduction potential were measured.

CRYSTAL STRUCTURE OF A 2D SHEET－LIKE μ－CYANIDO－OXAMIDATO BRIDGED Fe（III）－Cu（II） HETERNUCLEAR COMPLEX

The synthesis is and crystal structure are reported for the sheet-like compourd [CU2(oxpn)Fe(CN )5(NO)]. there oxpn is the dianion of M, M'-bis(3-aminopropyl)oxamide. This compound crustallizes in the orthogonal space group Puma. with a=11 .413(4), b=22.242(5), c=7.736(2) A, and Z=4.The structure was refined to conventionat discrepancy factors R=0.047 and Pw=0.054. The Cu(II ) and Fe(III)centers are bridged by oxpn and cyanide, the formal behaves as a his-terdentate tigand bound to cooper(II)ion to form (II) dimers. whereas the latter bridges Cu(II) and Fe(III) centers in both symmetric and asymetric end- to-end bis-monodentate fashions, spreading out along be plane to form a 20 network. The Structure is made up of CuFe unit with Cu(II) and Fe(III) ions locating in a distorted square-based pyramid and a compressed octahedron, respectively.

Synthesis, characterization, and stability of iron (III) complex ions possessing phenanthroline-based ligands

It has previously been demonstrated that phenanthroline-based ligands used to make gold metallotherapuetics have the ability to exhibit cytotoxicity when not coordinated to the metal center. In an effort to help assess the mechanism by which these ligands may cause tumor cell death, iron binding and removal experiments have been considered. The close linkage between cell proliferation and intracellular iron concentrations suggest that iron deprivation strategies may be a mechanism involved in inhibiting tumor cell growth. With the creation of iron (III) phen complexes, the iron binding abilities of three polypyridal ligands [1,10-phenanthroline (phen), 2,9-dimethyl-1, 10-phenanthroline (methylphen), and 2,9-di-sec-butyl-1, 10-phenanthroline (sec-butylphen)] can be tested via a competition reaction with a known iron chelator. Therefore, iron (III) complexes possessing all three ligands were synthesized. Initial mass spectrometric and infrared absorption data indicate that iron (III) tetrachloride complex ions with protonated phen ligands (RphenH+) were formed: [phenH][FeCl4], [methylphenH][FeCl4], [sec-butylphenH][FeCl4]. UV-vis spectroscopy was used to monitor the stability of the complex ions, and it was found that the sec-butylpheniron complex was more stable than the phen and methylphen analogues. This was based on the observation that free ligand was observed immediately upon the addition of EDTA to the [phenH][FeCl4] and [methylphenH] [FeCl4] complex ions.

Periodate Oxidation of a Ternary Complex of Nitrilotriacetatochromium(III) Involving ß-Alanine as Co-Ligand

The kinetics of the periodate oxidation of chromium(III)-complex, [CrIII(NTA)(Ala)(H2O)]-(NTA = Nitrilotriacetate and Ala = ß-alanine) to Cr(VI) have been carried out for the temperature range 15°C - 35°C under pseudo-first order conditions, >>?[complex]. Reaction obeyed first order dependence with respect to and [Cr(III)], and the rate of reaction increases with increasing of pH for the range 3.40 - 4.45. Experimentally, the mechanism of this reaction is found to be consistent with the rate law in which the hydroxo species, [CrIII(NTA)(Ala)(OH)]2- is considerably much more reactive than their conjugate acid. ΔH* and ΔS* have been calculated. It is proposed that electron transfer occurs through an inner-sphere mechanism via coordination of to chromium(III).

FERROMAGNETICALLY COUPLED Gd(III)Cu(II)Gd(III)TRINUCLEAR COMPLEXES

Three new heterotrinuclear complexes have been synthesized and characterized, namely {[Gd(L)(2)](2)[Cu(pbaOH)]}(ClO4)(4), where pbaOH denotes 2-hydroxy-1,3-propylenebis(oxamato), L stands for 1,10-phenanthroline (phen), 5-nitro-1,10-phenanthroline (NO2-phen) or 2,2'-bipyridyl (bpy). The temperature dependence of the magnetic susceptibility of ([Gd(phen)(2)(ClO4)](2)[Cu(pbaOH)])(ClO4)(2) has been studied in the 4-300K range, giving the exchange integral J = 6.69 cm(-1). This indicates a weak ferromagnetic interaction between the copper(II) and gadolinium(III) ions.

Kinetics on Thermal Decomposition of Iron(III) Complexes of 1,2-Bis(Imino-4’-Antipyrinyl)Ethane with Varying Counter Anions

A comparative thermal decomposition kinetic investigation on Fe(III) complexes of a antipyrine Schiff base ligand, 1,2-Bis(imino-4’-antipyrinyl)ethane (GA)), with varying counter anions viz. CIO4-, NO3-, SCN-, Cl-, and Br-, has been done by thermogravimetric analysis by using Coats-Redfern equation. The kinetic parameters like activation energy (E), pre-exponential factor (A) and entropy of activation (ΔS) were quantified. On comparing the various kinetic parameters, lower activation energy was observed in second stage as compared to first thermal decomposition stage. The same trend has been observed for pre-exponential factor (A) and entropy of activation (ΔS). The present results show that the starting materials having higher activation energy (E), are more stable than the intermediate products, however;the intermediate products possess well-ordered chemical structure due to their highly negative entropy of activation (ΔS) values. The present investigation proves that the counter anions play an important role on the thermal decomposition kinetics of the complexes.

Spectrophotometric Characterization of the Complex Generated in Solution for the Reaction of H[Ru(III)Cl₂(H₂EDTA)] Complex with AETS Modifier Agent

Spectrophotometric method was used to evaluate the kinetic of the complex formation from the reaction between H[Ru(III)Cl2(H2EDTA)] and the modifier agent [3-(2-aminoethyl)aminopropyl] trimethoxysilane (AEATS) (μ = 0.50 mol.dm-3 with NaCF3COO, 298.15 K), in pseudo-first order conditions. These studies showed that the reactions are successives producing several species influenced by the concentrations ratio. The electronics spectrum of all solutions showed a band in 457 nm with variable molar absorptivity (ε).

Immp2l Mutation Induces Mitochondrial Membrane Depolarization and Complex Ⅲ Activity Suppression after Middle Cerebral Artery Occlusion in Mice

Objective We previously reported that mutations in inner mitochondrial membrane peptidase 2-like(Immp2l)increase infarct volume,enhance superoxide production,and suppress mitochondrial respiration after transient cerebral focal ischemia and reperfusion injury.The present study investigated the impact of heterozygous Immp2l mutation on mitochondria function after ischemia and reperfusion injury in mice.Methods Mice were subjected to middle cerebral artery occlusion for 1 h followed by 0,1,5,and 24 h of reperfusion.The effects of Immp2l^(+/−)on mitochondrial membrane potential,mitochondrial respiratory complex III activity,caspase-3,and apoptosis-inducing factor(AIF)translocation were examined.Results Immp2l^(+/−)increased ischemic brain damage and the number of TUNEL-positive cells compared with wild-type mice.Immp2l^(+/−)led to mitochondrial damage,mitochondrial membrane potential depolarization,mitochondrial respiratory complex III activity suppression,caspase-3 activation,and AIF nuclear translocation.Conclusion The adverse impact of Immp2l^(+/−)on the brain after ischemia and reperfusion might be related to mitochondrial damage that involves depolarization of the mitochondrial membrane potential,inhibition of the mitochondrial respiratory complex III,and activation of mitochondria-mediated cell death pathways.These results suggest that patients with stroke carrying Immp2l^(+/−)might have worse and more severe infarcts,followed by a worse prognosis than those without Immp2l mutations.

九配位钇(III)-氨三乙酸配合物K_3[Y(NTA)2(H2O)]·6H_2O的合成及分子结构

：In this paper we describe the molecular and crystal structures of the K3[Y(NTA)2(H2O)]· 6H2O(H3NTA=nitrilotriacetic acid). The crystal data are as follows: monoclinic system, C2/c space group, a=1.5268(3)nm,b=1.2833(3)nm,c=2.6079(5)nm,β =96.03(3)° ,V=5.0815(18)nm3,Z=8,M=708.68,Dc=1.852gcm-3,μ =2.875mm-1,F(000)=2880.The final R1 and wR2 are 0.0636 and 0.1523 for 4264 [I >2.0σ (I)] unique reflections and 0.1178 and 0.1651 for all 4364 reflections,respectively.In the title complex, the anion [Y(NTA)2(H2O)]3- has a nine-coordination structure with distorted monocapped square antiprism. Each group acts as a tetradentate ligand with three O atoms and one N atom and a H2O molecule caps a quadrilateral face as a ligand.It can be known that the Y(III) ion can form a high-coordinate compound with aminopolycarboxylic acid ligands because it has a larger ionic radius (0.104nm).

环金属配体Ir(Ⅲ)配合物结构、光谱和量子效率的理论研究

对一类环金属Ir(Ⅲ)[(C^N)_(2)Ir(A^A)]配合物[C^N=ptaz(1,2,4),mhtz(3),ptaz=3,4,5-三苯基-4H-1,2,4-三唑,mhtz=1,3-双甲基-5-苯基-1H-1,2,4-三唑;A^A=pzpy(1),npzpy(2,3),bicb(4),pzpy=2-(1H-吡唑-1-基)吡啶,npzpy=4-二甲基氨基-2-(1H-吡唑-1-基)吡啶,bicb=3,3′-亚甲基双(1-甲基-1H-咪唑-2-亚基)]的结构、光谱特征和磷光量子效率进行了理论研究.计算方法探究表明,基于B3LYP泛函优化的基态结构和单激发组态相互作用(CIS)方法得到的激发态结构计算的吸收和发射光谱更准确.配合物1~4的最低吸收峰和发射峰分别位于408,376,382,365 nm和503,506,468,511 nm处,其HOMOs主要由金属和C^N配体占据,而配合物1~3的LUMOs由A^A配体的π反键轨道组成,配合物4的LUMO存在于C^N配体上.因此,配合物4的最低吸收峰和发射峰具有与配合物1~3不同的金属到配体和配体内部(MLCT/ILCT)的混合跃迁性质,非共轭N^N配体的引入显著消弱了其在跃迁过程中的贡献程度.配合物1~4的量子效率取决于非辐射跃迁速率常数k_(nr),这与它们重组能的贡献[4569 cm^(-1)(3)>2583 cm^(-1)(1)>1232 cm^(-1)(2)>975 cm^(-1)(4)]相一致,表明主配体的体积和辅助配体的共轭能力都能影响配合物的磷光量子效率.

九配位(NH_4)_3[Y^III(ttha)]·5H_2O配合物的合成及结构

报道了含有自由羧酸基的新型稀土金属离子YIII氨基多羧酸配合物的合成及分子结构和晶体结构的测定 .具体结果如下 :分子式 (NH4 ) 3 [YIII(ttha) ]·5H2 O(ttha =三乙四胺六乙酸 ) ,单斜晶系 ,P2 (1) /c空间群 ,a =1.0 2 89(2 )nm ,b =1.2 75 7(3)nm ,c=2 .3184(5 )nm ,β =90 .92 (3)°,V =3.0 42 7(11)nm3 ,单位晶胞中的分子数为 4,Dc=1.5 75g·cm-3 ,μ =2 .0 0 2mm-1和F(0 0 0 ) =15 12 ,对 5 145个独立的衍射点它的R和Rw值分别为 0 .0 5 14和 0 .12 87,对所有5 2 85个衍射点它的R和Rw值分别为 0 .10 85和 0 .140 7.在配合物离子 [YIII(ttha) ]3 -中 ,YN4 O5部分是九配位变形的单帽四方反棱柱体结构 .其中的COO-是一个未参与配位的可用于修饰的自由羧酸基 .由此可知90 YIII ttha配合物通过修饰与具有定向功能的生物大分子等相接可形成定向放射性抗肿瘤药物 .