Tautomerism of the metal complexes with 1-amino-4-hydroxyanthaquinone

Diversity of electronic absorption spectra of the metal complexes with 1-amino-4-hydroxyan-thraquinone is a consequence of the fact that they exist as equilibrium mixtures of tautomers with the isomeric quinoid structure of the ligand. These complexes are characterized by keto-oxide and amino-imine tautomerism, and samples of the complexes differ by composition of the tautomers.     

Preparation of 1-amino-4-methylpiperazine

The selectivity of the formation of N-di(2-chloroethyl)methylamine in reactions with various chlorinating agents has been investigated and the optimum chlorinating agent has been found. 1-Amino-4-methylpiperazine has been obtained for the first time by the cyclization of N-di(2-chloroethyl)methylamine with aqueous hydrazine. A possible mechanism has been proposed for the cyclization reaction.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1794–1797, December, 2004.     

4-Cyanoaniline complexes with transition metal(II) halides

Summary Coordination compounds formed by the interaction of manganese(II), cobalt(II), nickel(II) and copper(II) chloride and bromide with 4-cyanoaniline (4-CA) have been prepared and characterized by molar conductance, magnetic susceptibilities, electronic and i.r. spectral measurements down to 200 cm^–1 in the solid state. The isolated complexes are M(4-CA)₂X₂ except for nickel(II) bromide which is NI(4-CA)₄Br₂. I.r. spectra, indicate that 4-CA, though a potentially bidentate ligand, nevertheless acts only as a terminally aniline (NH₂) bonded monodentate ligand in all the complexes. Tentative stereochemistries of the complexes have been suggested in the solid state.     

Quinoxaline 1-oxide complexes with transition metal chlorides[1]

3d metal chloride complexes with quinoxaline 1-oxide (NQxO) were prepared by allowing ligand and salt solutions, pretreated with molecular sieve 4A, to interact. Complexes of the following stoicheiometries were obtained: (CrCl₃)(NQxO)₃·12H₂O, MNCl₂(NQxO)₂, (FeCl₃)(NQxO)₃·2H₂O, CoCl₂(NQxO)₃·5H₂O, NiCl₂(NQxO)₂, CuCl₂(NQxO)₂·3H₂O and ZnCl₂(NQxO). Characterization of the new metal complexes was based on spectral and magnetic studies. The overall evidence suggests that these compounds are bi- or poly-nuclear. Likely structures involve: Both terminal and bridging unidentate O-bonded NQxO and chloro ligands for the Cr(III) and Fe(III) complexes; chloride bridging and exclusively therminal NQxO for the Mn(II), Ni(II), and Cu(II) compounds; NQXO appears to be O-bonded in the Mn(II) and N-bonded in the Ni(II) and Cu(II) complexes; the Zn(II) complex contains terminal chloro and bridging dibentate, O, N-bonded NQxO; and the Co(II) compound appears to involve both terminal, N-bonded, and bridging bidentate, O, N-bonded NQxO. The Zn(II) complex is probably tetrahedral, the Mn(II) compound pentacoordinated, and the rest of the new complexes hexacoordinated. With the exception of the Fe(III) complex, which probably involves spin-free-spin-paired equilibria (μ_eff = 3.71 BM), the new metal complexes are magnetically normal high-spin compounds.     

异羟肟酸过渡金属配合物对对氯甲苯催化氧化性能的研究

考察了N-羟基-N-苯基苯甲酰胺的钴、锰和铜配合物在对氯甲苯液相氧化生成对氯苯甲酸反应中的催化性能.考察了反应温度、催化剂浓度、中心金属离子、以及助催化剂对催化氧化反应的影响,发现以钴配合物为催化剂,反应温度为140℃,催化剂浓度为1.0 × 10-3 mol·L-1为最佳反应条件.添加NaBr和四甘醇能促进对氯甲苯的...     

Divalent transition metal complexes

4-(4-ethoxy-phenylhydrazono)-1-phenyl-3-methyl-1H-pyrazolin-5(4H)-one (5a) (H-EMPhP) as ligand and its Cu(II), Co(II) and Ni(II) complexes 4(a-c) were synthesized and characterized by their thermal and spectral properties. The azocoupling product (H-EMPhP), able of azo-hydrazone tautomerism 5(a-d), act as a bidentate ligand involving in coordination the azogroup nitrogen of its common anion (7) and the oxygen atom that is bound to the pyrazole ring of the mentioned anion (7).     

Magnetic properties of new complexes of 3d metal chlorides with 3-amino-4-ethoxycarbonylpyrazole

New complexes of Co(II), Ni(II), and Cu(II) chlorides with 3-amino-4-ethoxycarbonylpyrazole (L) of the composition ML₂Cl₂ are synthesized. The compounds are studied by powder X-ray diffraction, electronic and IR spectroscopy, static magnetic susceptibility (temperature range 2–300 K). It is found that in the ML₂Cl₂ complexes (M = Co(II), Ni(II), Cu(II)) ferromagnetic exchange interactions between the unpaired electrons of metal ions occur. In [CoL₂Cl₂] and [NiL₂Cl₂] compounds a transition to the magnetically ordered state (T _c ? 10–12 K) is observed.     

New bis-macrocyclic complexes with transition metal ions

Template condensation of benzidine, formaldehyde, ethylenediamine or 1,3-diaminopropane, metal salt and 1-phenyl-1,3-butanedione or 2,3-butanedione in a 1:4:2:2 molar ratio results in the formation of two new series of binuclear pentaaza macrocyclic complexes: dichloro[1,1-phenylbis(7-methyl-9-phenyl-1,3,6,10,13-pentaazacyclotetradeca-6,9-diene) metal(II)], [M₂LCl₄] (M = Co^II, Cu^II, Fe^III and Zn^II) and dichloro[1,1-phenylbis(8,9-dimethyl-1,3,7,10,14-pentaazacyclopentadeca-7,9-diene) metal(II)], [M₂LCl₄] (M = Ni^II, Co^II, Cu^II and Cd^II). Both series were characterized by i.r., ¹H-n.m.r., u.v.–vis. spectral studies, conductivity and magnetic susceptibility measurements.     

Some transition metal nitrate complexes with hexamethylenetetramine

Three hexamethylenetetramine (HMTA) metal nitrate complexes such as [M(H₂O)₄(H₂O-HMTA)₂](NO₃)·4H₂O (where M=Co, Ni and Zn) have been prepared and characterized by X-ray crystallography. Their thermal decomposition have been studied by using dynamic, isothermal thermogravimery (TG) and differential thermal analysis (DTA). Kinetics of thermal decomposition was undertaken by applying model-fitting as well as isoconversional methods. The possible pathways of thermolysis have also been proposed. Ignition delay measurements have been carried out to investigate the response of these complexes under condition of rapid heating.     

Preparation and properties of anionic transition metal complexes containing triheterocarbenium ions

Summary Thermally stable anionic tetracarbonylcobalt complexes containing triheterocarbenium ions, [Co(CO)₄]^–[cation]⁺, have been synthesized by the ion exchange reaction of [Co(CO)₄]^–PPN⁺ with the corresponding carbenium ions. Similar molybdenum complexes containing cyclopentadienyl and carbonyl ligands were also prepared. The complexes were characterized by elemental analyses and by i.r. and n.m.r. spectroscopies. The ionic structures of the complexes are confirmed on the basis of their large electric conductivities.     

过渡金属-4, 4'-联吡啶配合物的合成及其晶体结构

由过渡金属与4,4'-联吡啶反应,得到两种新型配合物[Zn(4,4'-bpy)~2(H~2O)~2](pic)~2·(4,4'-bpy)·(H~2O)(1)与[Cu(4,4'-bpy)(pic)~2](2)(4,4'bpy:4,4'-联吡啶,pic^-:苦味酸根),进行了元素分析、红外光谱、X射线衍射等表征。X射线衍射结果表明,晶体1属单斜晶系,空间群为C~c,晶胞参数为：a=2.2716(2)nm,b=1.6191(3)nm,c=1.6166(2)nm,β=131.085(7)°,V=4.481(2)nm^3,Z=4;该配合物由4,4'-联吡啶与金属配位形成多孔的二维网,二维网再由未配位的4,4'-联吡啶通过氢键作用沿a方向堆积得三维网状结构,未配位的4,4'-联吡啶、水、苦味酸根离子就被包含在这种网络之中,展示出一定的包合现象,晶体2属三斜晶系,空间群为P1,晶胞参数为：a=0.6100(2)nm,b=1.0186(3)nm,c=1.1046(2)nm,α=107.230(10)°,β=101.992(2)°,γ=97.87(7)°,V=0.6266(3)nm^3,Z=1。在该配合物中,4,4'-联吡啶分子、苦味酸根离子均与铜离子配位,形成一维链状结构。     

Preparation and thermal behaviour of divalent transition metal complexes of pyromellitic acid with hydrazine

Hydrazine forms two different types of complexes with divalent metal ions and pyromellitic acid (H₄pml) in aqueous medium: (i) hydrazinium complexes of formulae, (N₂H₅)₂M(pml)·xH₂O, where x = 3 for M=Ni and x = 4 for M=Co or Zn, and (N₂H₅)₂Mn(H₂pml)₂, at pH 4.5, (ii) neutral hydrazine complexes with formulae, M₂(pml)(N₂H₄) _n ·xH₂O where M=Co or Ni when n = 4 and x = 5 or 4 and M=Zn or Cd when n = 2, and x = 4 or 3 at pH 7, and M(H₂pml)(N₂H₄)·xH₂O where x = 4; M=Cu and x = 0; M=Hg, at pH 3, 7.5, respectively. All the complexes are insoluble in water, alcohol and ether. The N–N stretching frequency (990–1,007 cm⁻¹ for coordinated hydrazinium ion and 956–985 cm⁻¹ for bridged neutral hydrazine) indicates the nature of hydrazine present in the complexes. Simultaneously TG-DTA analysis indicates that hydrazinium complexes undergo dehydration and dehydrazination in a single step endothermally in the range of 289–300 °C whereas neutral hydrazine complexes undergo endothermic dehydration (~100 °C) followed by exothermic dehydrazination in the temperature range, 253–332 °C. The anhydrous metal carboxylates further decompose exothermally to leave the respective metal oxides or metal carbonates except zinc, which gives its oxalate as the end product. X-ray powder patterns indicate that even the complexes with the same formulation possess no isomorphism.     

Thermoanalytical study of selected transition bivalent metal complexes with 5-carbaldehyde-4-methylimidazole

To compare thermal stability of Co(II), Zn(II), and Cd(II) complexes with 4-CHO-5-MeIm, the two compounds of formula [MnL₂(NO₃)₂] and [NiL₃](NO₃)₂ have been prepared and structurally characterized. Elemental analysis and spectroscopic studies have confirmed a bidentate fashion of coordination of the ligand to Mn(II) and Ni(II) ions. IR and Raman spectra indicate that there are different coordination modes of the NO₃ ^? in compounds: non-coordinated and coordinated. The decomposition process of the studied complexes in nitrogen and argon (Ni(II) complex) atmosphere proceeds in three main stages, except Zn(II) complex, in temperature range 353?C1163?K. The final products of decomposition are CoO, MnO, Cd, ZnN₄, NiN₃. In addition, we have to admit that the different coordination mode of the NO₃ ^? ions in complexes: non-coordinated (in the (1), (4), and (5)) and coordinated (in the (2) and (3)) correlate with its thermal behavior. Thus, temperature ranges of its decompositions are observed: below 533?K and above 533?K, respectively. In Co(II), Mn(II), and Cd(II) complexes the fragments of N-donor atom-containing ligands decompose in the last stages, contrary to Zn(II) and Ni(II) compounds, in which metal ion surrounded by N atoms remains until the end. The course of pyrolysis and molecular structure of the complexes lead to the same conclusion about the strength of metal?Cligand bonds. On the basis of obtained results, it is concluded that the thermal stability of the studied compounds follows the order: (1)?<?(5)?<?(2)?<?(3)?<?(4).     

Stability of transition metal complexes with sulfonated polymers

Stability constants of macromolecular metallocomplexes of transition metal ions (Ag⁺, Cu²⁺, Ni²⁺, Fe³⁺) with sulfonated polymers in water and aqueous HCl and NaCl solutions were determined from quenching by transition metal ions of the luminescence of macromolecules labeled with luminescent groups.     

Polyoxometalate tri-supported transition metal complexes containing mixed-valent transition metal ions

Three compounds, [AsMo₈V₆O₄₂][Cu(2,2?-bpy)₂]₂[Cu(2,2?-bpy)]·4H₂O (1), [PMo₈V₆O₄₂][Cu(2,2?-bpy)₂]₂[Cu(2,2?-bpy)]·3H₂O (2) and [PMo₈V₆O₄₂][Cu(2,2?-bpy)₂]₂[Cu(2,2?-bpy)]·3.5H₂O (3), have been synthesized under hydrothermal conditions and characterized by IR, UV–vis, XRD, TG, elemental analysis, and X-ray diffraction analysis. Single-crystal X-ray structure analysis reveals that 1 and 2 are isostructural and isomorphous, whereas 2 and 3 are polymorphs. Polymorphs of 1 have not been synthesized yet. The mixed-valent transition metal ion in 1–3 has been further confirmed by TG analyses. Catalytic properties of 1 and 2 have also been studied.     

Bridging vinylalkylidene transition metal complexes

Vinylalkylidene transition metal complexes have been extensively used as ‘multitalent tools’ in organic synthesis, covering a broad field of applications. The vinylalkylidene ligands can be monodentate; alternatively they can adopt a bridging coordination mode in complexes with two adjacent metal atoms. As for other unsaturated organic ligands which can bond in both mono- and di-nuclear modes, the bridging coordination can give rise to new and different chemical properties from those found when the ligand is bound to a single metal centre. Likewise, the synthetic routes to bridging vinylalkylidene complexes offer a broader range of possibilities compared to those used to make mononuclear vinylalkylidenes. In spite of the fact that bridging vinylalkylidene complexes have been known for about 40 years, their synthetic potential as C₃ activated fragments has so far been under-exploited. Comparison with other C₃ bridged ligands (allenyls and allyls) indicates that vinylalkylidene ligands are reactive and versatile species. This review article gives an overview of the chemistry of bridging vinylalkylidene complexes to focus attention on their potential as synthetic tools.     

Fluorenone hydrazine-S-benzyldithiocarbazate transition metal complexes

Summary New Cu^II, Co^II, Ni^II, Cd^II, Zn^II, Hg^II, Pd^II and UO ₂ ^II complexes of the Schiff base ligand (FBz) formed by condensation of fluorenone withS-benzyldithiocarbazate have been prepared and characterized by elemental analysis, magnetic and spectroscopic measurements. The Cu(FBz)₂(Cl)₂ complex is paramagnetic. The Ni(FBz-H)₂ complex is diamagnetic, four-coordinate and square planar. The Co^II ion is oxidized in the presence of the Schiff base with the concomitant formation of Co^III complex of empirical formulae Co(FBz)Cl₃OH₂. The ligand was tested as a corrosion inhibitor for copper. Inhibition efficiency was calculated and the limiting concentration of FBz to give maximum efficiency was 10^–3 mol dm^–3 at 25°C. The polarographic reduction of FBz was investigated in Britton-Robinson buffer solutions of pH 3–10. The polarograms at dme indicated that the depolarizer is reduced through two two-electron irreversible diffusion-controlled waves. The mechanistic pathway of the electrode reaction is commensurate with this result.