1,4,7-三氮杂环癸烷过渡金属配合物的合成与结构表征

以十元环大环三胺配体1,4,7-三氮杂环癸烷(tacd)为主配体,分别与钴、镍、铜和锌的顺丁烯二酸盐和己二酸盐进行反应,得到了8种含有双大环的单核配合物,利用元素分析,红外光谱以及热重分析等手段对它们的结构进行了表征.结果表明这八种配合物具有类似的配位结构.     

含二茂铁基Schiff碱及其过渡金属配合物的合成与表征

合成了两个新型含有二茂铁基的schiff碱配体及其8种过渡金属配合物,并通过^1HNMR,IR,元素分析,热分析和摩尔电导对其结构进行表征,提出了配合物的可能结构。     

氮支冠醚二硫代甲酸根过渡金属配合物的合成和性质

氮支冠醚二硫代甲酸根过渡金属配合物的合成和性质     

西佛碱型大环多胺过渡金属配合物的合成与表征

西佛碱型大环多胺过渡金属配合物的合成与表征     

多二茂铁基二氮杂己烷及其过渡金属配合物的合成

乙二胺与二茂铁甲醛或双二茂铁甲基氟硼酸盐反应，合成了１，６－二（二茂铁基）－２，５－二氮杂己烷和１，１，６，６－四（二茂铁基）－２，５－二氮己烷，它们与过渡金属（Ｆｅ＾２＋，Ｃｏ＾２＋，Ｎｉ＾２＋，Ｃｕ＾２＋，Ｚｎ＾２＋）盐在乙醇或乙醇－二氯甲烷中反应，是１４种过渡金属配合物，对这些化合物进行了表征，二种配体及其铜配合物用作复合固体推进剂的燃速调节剂时，基本不迁移，而燃速催化效率均超过辛基二茂铁。     

Synthesis and Structural Characterization of Three Novel Macrocyclic Coordination Complexes Formed by Self-assembly of Bridged Bi-or Tetrapyridine with Transition Metal Salts

Serf-assembly of a ferrocenyl-bridged bipyridine ligand bpef [bpef=1, 1＇-bis（trans-2-pyrid-4＇-ylethenyl）ferrocene] with silver triflate in CH2Cl2/MeOH or mercuric diiodide in MeCN/CH2Cl2 gave the corresponding macrocyclic coordination complexes [bpef]2[AgSO3CF3]2 （1） and [bpef]2[Hg3I6] （2） in 93% and 89% yields, respectively, whereas the pentaerythritolyl-bridged tetrapyridine ligand ptpc [ptpc=pentaerythritol tetrakis-（4-pyridinecarboxylate）] reacted with cobalt thiocyanate via self-assembly to afford the macrocyclic coordination polymer [Co（NCS）2（ptpc）], （3） in 90% yield. The X-ray diffraction analyses for 1-3 confirmed their novel macrocyclic structures and revealed that （i） the two silver atoms in complex 1 have an essentially linear geometry with N-Ag-N bond angle of 175.7° and 172.9°, （ii） the geometry of the middle mercury atom in complex 2 is square-planar, while the other two mercury atoms in the other two complexes are tetrahedral, and （iii） all the cobalt atoms in complex 3 adopt an octahedral geometry. In addition, the synthetic procedure for the known tetrapyridine ligand ptpc has been improved.     

IIB族金属二硫代氨基甲酸配合物的合成、表征及热稳定性研究

在甲醇溶液中合成了一系列IIB过渡金属Zn(II), Cd(II)的二羟乙基二硫代氨基甲酸[(EtOH)₂dtc]的配合物, 并对配合物M[(EtOH)₂dtc]₂L [M＝Zn (1), Cd (2), L＝2,2'-联吡啶; M＝Zn (3), Cd (4), L＝邻菲啰啉]进行了红外光谱、元素分析、热重分析表征工作. 热重分析表明配合物1～4中DTC配体比中性配体更易失去, 热分解最终产物为相应的氧化物. 对化合物1, 2做了X-ray单晶衍射分析, 1为单斜晶系, P2₁/c空间群, 晶胞参数a＝0.72146(5) nm, b＝2.61720(18) nm, c＝1.59438(11) nm,b＝97.899(2)°, V＝2.9820(4) nm³, Z＝4, m＝1.133 mm^－1, D_c＝1.297 Mg•m^－3; 2为三斜晶系, P-1空间群, 晶胞参数a＝1.0075(2) nm, b＝1.1580(2) nm, c＝1.1777(2) nm, a＝70.92(3)°, b＝85.71(3)°, γ＝81.02(3)°, V＝1.2822(4) nm³, Z＝2, m＝2.118 mm^－1, D_c＝1.630 Mg•m^－3.     

Hydrolytic Ring Opening Reactions of Pyromellitic Dianhydride for Divalent Transition Metal Carboxylate Complexes

The hydrolytic ring opening reactions of pyromellitic dianhydride is an effective method to prepare transition metal carboxylate complexes. In this paper, two dinuclear complexes [Ni₂(2,2′‐bipy)₂(btec)(H₂O)₆] · 2H₂O ( 1 ) and [Cd₂ (phen)₄(H₂O)₂(H₂btec)] · H₂btec · 2H₂O ( 2 ) (H₄btec = 1,2,4,5‐benzenetetracarboxylic acid, phen = 1,10‐phenanthroline, and 2,2′‐bipy = 2,2′‐bipyridine) were synthesized by slow diffusion methods and their structures were determined byX‐ray structure analysis. In both structures metal atoms are in distorted octahedral environments and they are linked by bis‐monodentately coordinated 1,2,4,5‐benzentetracarboxylate ligands as bridging units. The crystalline compounds, which are insoluble in water as well as common organic solvents, have been characterized in the solid‐state by elemental analysis, thermogravimetric analysis, IR, and diffuse reflectance UV/Visspectroscopy. Moreover, the study of the physical properties of complex 2 demonstrates that it exhibits blue fluorescence emission in the solid state at room temperature.     

Synthesis,Structural, and Antibacterial Studies of Some Transition Metal Complexes Derived from Thiosemicarbazone and Semicarbazone

A series of metal complexes of Pd(II), Pt(II), Rh(III), Ir(III), and Ru(III) with thiosemicarbazone and semicarbazone of 2-acetyl thiophene have been synthesized. Their structures were determined on the basis of elemental analyses; molar conductance; magnetic susceptibility measurements; and IR, ¹ H NMR, and electronic spectral studies. On the basis of molar conductance, the complexes may be formulated as [M(L)₂]Cl₂ and [M′(L)₂Cl₂]Cl [where M = Pd(II), Pt(II) and M′ = Rh(III), Ir(III), and Ru(III)] due to their 1:2 and 1:1 electrolytic nature. On the basis of IR, ¹ West, D. X., Liberta, A. E., Padhye, S. B., Chikate, R. C., Sonawane, P. B. V., Kumbhar, A. S. and Yerande, R. G. 1993. Coord. Chem. Rev., 123: 49[Crossref], [Web of Science ®] , [Google Scholar]H NMR, and electronic spectral studies, an octahedral geometry has been assigned for Rh(III), Ir(III), and Ru(III), while square planar geometry has been assigned for the Pd(II) and Pt(II) complexes. The synthesized ligands and their complexes have been screened for bactericidal activity against several bacterial species (i.e., B. macerans, A. aureus, E. coli), and it is shown that the metal complexes act as more active antimicrobial agents than the uncomplexed ligands from which they derive.     

Synthesis,Structural Characterization and Preliminary Biological Studies of Several Heterocyclic Transition Metal Carbonyl Complexes

The reaction of molybdenum, tungsten and manganese carbonyls with several thiazole heterocycle ligands yielded a number of coordinated transition metal complexes 1 – 10 . Of these complexes 1 – 6 are new compounds which have not been reported to date. The structures of new compounds were characterized by FT‐IR and ¹H‐NMR spectroscopy as well as single‐crystal X‐ray diffraction analysis. Complexes 1 – 10 are carbon monoxide releasing molecules that show structure‐related anti‐cancer activity. The cytotoxicity of all compounds on Hela cells was evaluated by MTT assay, and the results show that carbon monoxide releasing molecules containing such Schiff base ligands may have biomedical applications for their anti‐tumor effect.     

Synthesis and Thermal Analysis of 2,2′-bipyridine Divalent Transition Metal Hexachloroplumbates

Several complex salts of the general formula [M(II) (bipy)_x(H₂O)_y]PbCl₆ (where x=2–3, y=0–2 and M=Mn(II), Fe(II), Ni(II), Co(II), Cu(II), Zn(II), Cd(II) and Hg(II)) were synthesized and investigated by DTA, TG and DTG. Some of the decomposition products were identified by IR spectroscopy and other methods. The compounds decompose with the liberation of water (in the case of hydrates), chlorine (sometimes causing chlorination of organic fragments), organic molecules (sometimes chlorinated) and sometimes hydrogen chloride. The residues comprise metal(II) chlorides and PbCl₂. This revised version was published online in August 2006 with corrections to the Cover Date.     

含硫席夫碱安息香缩肼基二硫代甲酸甲酯过渡金属配合物的合成与表征

合成和表征了新的含硫席夫碱—安息香缩肼基二硫代甲酸甲酯 (H2 L)及与Mn(Ⅱ ) ,Co(Ⅱ ) ,Ni(Ⅱ )Zn(Ⅱ )和Cd(Ⅱ )生成的配合物 [M(HL) 2 ]。结果表明这些配合物中安息香缩肼基二硫代甲酸甲酯存在为去质子化的烯硫醇式三齿配体 ,通过甲亚胺基氮原子、醇羟基氧原子和烯硫醇硫原子配位 ,金属离子处于六配位的八面体环境。     

系列过渡金属与三角架多咪唑配合物的合成、结构及表征

以三氨乙基胺和N－甲基咪唑醛为原料合成了三角架多咪唑配体((min)₃tren)，并合成了五个过渡金属配合物：[Zn(min)₃tren](ClO₄)₂1， [Cu(min)₃tren](ClO₄)₂2, [Ni(min)₃tren](ClO₄)₂3, [Co(min)₃tren](ClO₄)₂4, and [Mn(min)₃tren](ClO₄)₂CH₃CN 5，通过元素分析，摩尔电导率，红外和电子光谱确定了化合物的组成。对配合物4和5进行了晶体结构测定。结果表明，在这两个化合物中金属原子均处于扭曲的八面体配位环境，分别与三个亚胺氮原子和三个咪唑氮原子配位。配合物4和5的电化学研究表明在乙腈溶液中，有[Co-O₂]^n-和[Mn-O₂]^n-存在，认为4和5是很好的超氧化物清除剂。     

对二茂铁基苯甲醛双缩间苯二胺盐酸盐Schiff碱及其过渡金属配合物的合成与表征

合成了新的二茂铁基苯甲醛双缩间苯二胺盐酸盐Schiff碱[m-C6H4(NCH)2(Cp′FeCp)2]及其过渡金属配合物[m-C6H4(NCH)2(Cp′FeCp)2·MCl2(M=Pd2+,Fe2+,Zn2+)]。其结构经1HNMR,IR和元素分析表征。     

Synthesis,Structure and Characterization of Schiff Base Metal Complexes and Their Electrochemical Properties of Thionyl Chloride Reduction

A symmetric tetradentate Schiff base ligand bis(3‐methoxysalicylidene)‐o‐phenylenediamine (H₂L) was prepared. A series of transition metal complexes with this Schiff base ligand have been synthesized and structurally characterized by IR and elemental analysis. The catalysis for reduction of thionyl chloride was studied by means of constant resistance discharge. The result shows that [Mn(III)LCl(H₂O)]CH₃OH and [Co(II)HLCl(H₂O)] have a good catalytic activity for the reduction of thionyl chloride, which improves the cell voltage, the rate of discharge, and the lifetime of Li/SOCl₂ batteries.     

邻香草醛缩天冬氨酸铜、锌、钴、镍配合物的合成

氨基酸希夫碱是具有多种配位原子和生物、化学活性的配体,其过渡金属配合物对生物无机化学和医药有重要意义［１～３］,我们曾报道过某些氨基酸希夫碱及其配合物的抗Ｏ－·２性能［４,５］．本文合成了邻香草醛缩天冬氨酸铜、锌、钴、镍配合物并进行了系列表征,提出其...     

Synthesis and Structural Chemistry of Two Novel Transition Metal Organic Phosphonates

Two novel transition metal phosphonate compounds, [Co（H2BDPP）（phen）]n 1 （BDPP = p-O3PCH2（C6H4）CH2PO3, phen = 1,10-phenanthroline） and [Pb3（BCP）2]n 2 （BCP = OOC（C6H4）CH2PO3）, have been synthesized and structurally determined by X-ray single-crystal diffraction. Compound 1 crystallizes in the monoclinic system, space group C2/c with a = 21.169（4）, b = 12.001（2）, c = 7.6211（15）A, β = 98.03（3）°, V= 1917.2（6）A^3, C20H18N2O6P2Co, Mr = 505.22, Z = 8, De= 1.737 g/cm^3, p = 1.107 mm^-1, F（000） = 1020, the final R= 0.0450 and wR = 0.1306 for 2072 observed reflections （I 〉 2σ（I）. Compound 2 crystallizes in the monoclinic system, space group C2/c with a = 4.7167（9）, b = 18.753（2）, c = 22.781（3）A, β = 91.07（3）°, V= 2014.7（14）A^, C8H6O5PPb1.5, Mr = 523.88, Z = 8, Dc = 3.454 g/cm^3, p = 25.222 mm^-1, F（000） = 1856, the final R = 0.0441 and wR = 0.1906 for 2259 observed reflections （I 〉 2σ（I）. In compound 1, the 1D chain running along the c axis is bridged by four ligands （trans- HO3PCH2C6H4CH2PO3H） in four different directions to extend the structure into a three- dimensional network. In compound 2, the Pb（II） displays 4- and 5-coordination modes. There is a one-dimensional P-O-Pb band along the a axis formed by PO3 groups and Pb（II） cations. These bands are joined by μ2-O of -COO to yield two-dimensional inorganic P-O-Pb layers which are pillared by the OOCC6HaCH2PO3 ligands to form a three-dimensional network. Moreover, compound 2 displays a strong emission band attributed to the ligand-centered （LC） transition.     

铜二取代三元杂多化合物的制备、晶体结构和性质

The half Dawson structure complex has been prepared by reaction of Na₂WO₄·2H₂O, Na₂MoO₄·2H₂O and NaH₂PO₄ in water. [TBA]₄H₃[PW₆Mo₄Cu₂O₃₈(H₂O)₂] have been synthesized by reaction of [PW₅Mo₄O₃₄]^9- and Cu²⁺ in water and recrystallized in a mixed acetone/water solvent. They were characterized by elemental analyses, IR spectra and electronic spectra. The crystal structure of [TBA]₄H₃[PW₆Mo₄Cu₂O₃₈(H₂O)₂] has been determined by X-ray structure analysis for the first time, which belongs to trigonal with space group R-3, a=b=c=1.53081 (18) nm, α=β=γ=109.458(17)°, Z=1, D_c=3.141Mg·m^-3, R=0.0780, R_w=0.1480. The sites of the molybdenum, tungsten and copper atoms are disordered over 12 possible locations in the crystal, and the anion has a high symmetry due to the disorder of the molybdenum, tungsten and copper atoms. CCDC: 176656.     

希夫碱过渡金属配合物的合成及其荧光性能

合成了3,5-二氯水杨醛缩邻苯二胺配体(H2L);H2L与M(NO3)2(M=Cu,Ni,Zn)反应,合成了3种希夫碱过渡金属配合物ML。UV,1HNMR,IR和元素分析研究表明ML为四配位。用荧光激发光谱和发射光谱研究了H2L和ML的光物理性能,结果表明,H2L具有较强的荧光;ZnL具有较强的荧光和良好的热稳定性(分解温度达424.2℃)。     

金刚烷胺邻香兰素Schiff碱过渡金属配合物的合成与表征

合成了金刚烷胺邻香兰素Sch iff碱配体(C18H23NO2,以L表示)与过渡金属的6种新的配合物[MC l2L](M=Mn(Ⅱ),Co(Ⅱ),N i(Ⅱ),Cu(Ⅱ),Zn(Ⅱ),Cd(Ⅱ)),用元素分析、摩尔电导、红外光谱和热重分析表征了配合物的结构;讨论了配体与中心金属离子的键合情况并推测了配合物的结构,每一中心金属离子与Sch iff碱配体中的酚羟基氧、甲氧基氧及2个氯离子发生配位,其配位数为4.