Coordination polymers of VIV—MII (MII = Mn,Co, Ni,Cd) with ethylmalonate anions

Russian Chemical Bulletin - A series of heterometallic 1D coordination polymers {[MII(VIVO)(Etmal)2(H2O)5] ? 2 H2O}n (MII = Mn (1), Co (2), Ni (3), Cd (4)) were synthesized. These compounds...     

Synthesis, structure, and magnetic properties of heterometallic trinuclear complexes {MII��LnIII��MII} (MII = Ni, Cu; LnIII = La, Pr, Sm, Eu, Gd)

Trinuclear heterometallic complexes containing the {M₂Ln(Piv)₆(NO₃)} (M^II = Ni, Cu; Ln^III = Nd, Pr, Sm, Eu, Gd; Piv^? is the anion of pivalic acid) and {Cu₂Ln(Piv)₈)]^? (Ln^III = Eu, Gd) metal cores were synthesized, their structures and magnetic properties were studied. For the most compounds, it was shown that their magnetic properties can be interpreted taking no interaction of the 3d-metal ions and a lanthanide into account. Ferromagnetic exchange interactions were found to exist between the unpaired electrons of the paramagnetic centers in the exchange clusters of the gadolinium-containing heterometallic complexes {M-Gd-M} (M = Ni or Cu).     

Study of the state of uranogermanates MII(HGeUO6)2·6H2O in Aqueous Solutions (MII = Mn, Co, Ni, Cu, Zn)

The state of d-elements uranogermanates M^II(HGeUO₆)₂·6H₂O in aqueous salt solutions in a wide range of ionic strength, ionic composition, and acidity has been investigated. The pH ranges of the uranogermanates stability have been determined, and products of their transformation have been identified. Solubility, solubility equilibrium constant, and Gibbs energy of formation have been determined for the studied uranogermanates. Diagrams of uranium(VI), germanium(IV), and M(II) state in aqueous solutions and in equilibrium solid phases have been plotted.     

State of uranyl silicates MII(HSiUO6)2 ·6H2O (MII=Mn, Co, Ni, Cu, Zn) in aqueous solutions

Uranyl silicates with formula M^II(HSiUO₆)₂·6H₂O (M^II=Mn, Co, Ni, Cu, Zn) were investigated in aqueous solutions in the pH range of 0÷14. The pH interval was established where compounds preserve their composition and structure. It varies in the pH range of (3.5–4.0)÷(10.8–11.4) and depends on M^II type. Out of this pH interval investigated uranyl silicates convert to the compounds of other composition and structure, such as amorphous silica, polyuranates and hydroxides of 3d-transition elements. The solubility of M^II(HSiUO₆)₂·6H₂O was determined, it’s value changes on the several orders of magnitude from 10^?6 M in subalkali solutions to 10^?3 M in acid and strongly alkaline media. Using obtained experimental data the solubility products and solubility curves of uranyl silicates were calculated by mathematical modeling. Also the speciation diagrams of uranium (VI), silicon (IV) and M (II) in solutions and solids were plotted.     

Low frequency vibrational spectra of crystalline and glassy metaborates Ba2MII(B3O6)2 (MII  Mg,Ca, Ni,Co, Cd)

The low frequency vibrational spectra (Raman and IR) of crystalline metaborates Ba₂M^II(B₃O₆)₂ (M^II  Mg, Ca, Ni, Co, Cd) are interpreted on the basis of a factor group analysis and with the help of ²⁴Mg²⁶Mg and ⁴⁰Ca⁴⁴Ca isotopic shifts. The far-IR spectra of the glasses appear as the envelope of the spectra of the corresponding crystalline compounds for M^II  Mg, Ca and Cd, but they exhibit an additional broad absorption centred near 400 cm⁻¹ for M^II  Co, Ni and Zn. This absorption is assigned to a fourfold coordination of part of the M^II cations, the remaining being in sixfold coordination (as in the crystal) and responsible for a broad absorption in the 300-200 cm⁻¹ region. The possible existence of correlations between coordination and vibrational frequencies is discussed for either alkali and alkaline-earth cations, or transition elements.     

Study of the state of uranoarsenates MII(AsUO6)2·nH2O(MII = Mn2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Pb2+) in aqueous solutions

State of uranoarsenates M^II(AsUO₆)₂·nH₂O (M^II = Mn, Co, Ni, Cu, Zn, Cd, Pb) in aqueous solutions in a wide range of acidity (pH 0?C14) was studied. Acid-base boundaries of existence of the compounds were estimated, products of conversion were identified, and solubility of M^II(AsUO₆)₂·nH₂O was determined. On the basis of the obtained data the solubility products and Gibbs functions of formation of uranoarsenates, and the solubility curves were calculated, phase diagrams of uranium(VI) and arsenic(V) in solutions and in equilibrium solid phases were constructed with the use of the equilibrium thermodynamics technique.     

Isodimorphism of the salts 2RbCl · MIICl2 · 2H2O (MII = Mn,Fe, Co,Cu)

The three-component systems RbClMnCl₂H₂O, 2RbCl · CoCl₂ · 2H₂O2RbCl · CuCl₂ · 2H₂OH₂O, 2RbCl · CoCl₂ · 2H₂O2RbCl · MnCl₂ · 2H₂OH₂O have been studied at 25°C. In the 2RbCl · CoCl₂ · 2H₂O2RbCl · CuCl₂ · 2H₂OH₂O system, a discontinuous series of mixed crystals is formed and in the 2RbCl · CoCl₂ · 2H₂O2RbCl · MnCl₂ · 2H₂OH₂O system, a continuous series is present.The unit cell parameters of the 2RbCl · CoCl₂ · 2H₂O double salt were determined: a = 5.586(2) Å, b = 6.469(3) Å, c = 6.988(2) Å, α = 65.31(3)°, β = 87.69(3)°, γ = 84.65(4)°, volume 228.4 ų, Z = 1.The results obtained and discussed in conjunction with the crystal structure data suggest that for 2M^ICl · M^IICl₂ · 2H₂O type salts the triclinic structure is stable only when the large rubidium and cesium ions participate in combinations with non-Jahn-Teller metal(II) ions. In the cases of Jahn-Teller metal(II) ions or with potassium or ammonium ions a tetragonal structure is always stable.     

Heterometallic trinuclear {CdII—MII—CdII} pivalates (M = Mg,Ca, or Sr): ways of assembly and structural features

Conditions for chemical assembly of new heterometallic trinuclear pivalates [Cd₂M(piv)₆L₂] (M = Mg, Ca, or Sr; piv is pivalate) were found. Reactions with the nonchelating ligand 2,4-lutidine (lut) gave the crystals of heterometallic complexes [Cd₂M(piv)₆(lut)₂] (M = Mg (1), Ca (2), and Sr (3)). With the chelating ligand 1,10-phenanthroline (phen), only the homometallic dimer [Cd₂(piv)₄(phen)₂] (4) was obtained under these conditions. Yet heterometallic trinuclear complexes with 1,10-phenanthroline ([Cd₂Mg(piv)₆(H₂O)(phen)₂] (5), [CaCd₂(piv)₆(phen)₂] (6), and [Cd₂Sr(piv)₆(phen)₂]?2MeCN (7)) were synthesized by reactions of phen with complexes 1—3. For all the complexes obtained, the molecular and crystal structures as well as the details of their molecular architecture were determined. The thermal behavior of aqua complex 5 was studied by TG and DSC. The complex eliminated the water molecule between 130 and 180 °C with a high endothermic effect (Q = 101 kJ mol^–1) due to (1) intramolecular hydrogen bonds that stabilize its molecular architecture and (2) subsequent structural rearrangements.     

Synthesis and characterization of MIIU3O10 · nH2O (MII = Mg, Mn, Co, Ni, Cu, Zn, Cd) triuranates

Individual crystalline phases of composition M^IIU₃O₁₀ · nH₂O were prepared by reacting schoepite UO₃ · 2.25H₂O with aqueous solutions of Mg, Mn, Co, Ni, Cu, Zn, or Cd nitrates under hydrothermal conditions at 200°C. The composition and structure of the resultant compounds were determined by hightemperature X-ray diffraction, IR spectroscopy, scanning calorimetry, and chemical analysis; the dehydration and thermal destruction of the compounds were studied.     

New transition metal sulfates templated by 1,4-butanediamine, (C4H14N2)[MII(H2O)6](SO4)2·4H2O (MII: Co,Ni): Structure,reactivity and thermal decomposition

Two new hybrid materials, (C₄H₁₄N₂)[M^II(H₂O)₆](SO₄)₂·4H₂O (M^II: Co (I), Ni (II)), have been synthesised by slow evaporation method at room temperature and crystallographically characterized. They crystallise isotypically in the monoclinic system, space group P2₁/n, with the following unit-cell parameters a = 9.2285(3), b = 11.3333(4), c = 10.6693(4) Å, β = 109.004(2)°, Z = 2 and V = 1055.07(6) Å³ for I and a = 9.2127(2), b = 11.3182(2), c = 10.6434(2) Å, β = 109.094(1)°, Z = 2 and V = 1048.74(4) Å³ for II. The structure of the two supramolecular compounds consists of metallic cation octahedrally coordinated to six water molecules, sulfate anions, 1,4-butanediammonium cation and water molecules linked together via two types of hydrogen bonds, O–H?O and N–H?O. The two compounds are not stable at room temperature and their partial dehydration depends on the humidity of the environment. The thermal decomposition of precursors, studied by thermogravimetric analysis (TG) and temperature-dependent X-ray diffraction (TDXD), shows successive intermediate hydrates and crystalline anhydrous compounds upon dehydration.     

First heterobimetallic MnII/MII(M = Cu,Ni) complexes with open-chain aliphatic schiff-base ligands obtained by direct template synthesis

Four new heterobimetallic complexes [CuL¹][MnCl₄] (1), [CuL²][MnCl₄] (2), [NiL¹][MnCl₄] (3), [NiL²][MnCl₄] (4) (L¹?=?4,6,6-trimethyl-1,9-diamino-3,7-di-aza-nona-3-ene; L²?=?1,15-dihydroxy-7,9,9-trimethyl-3,6,10,13-tetra-aza-pentadeca-6-ene) have been prepared from elemental metals, ethylenediamine dihydrochloride or its N-(2-hydroxyethyl) derivative and acetone by the template condensation reaction. All complexes have been characterized by elemental analysis, IR and UV-Visible spectroscopy. The structures of 2 and 3 have been determined by X-ray crystallography (2: Orthorhombic, Pna2 _1, a?=?20.136(4), b?=?11.185(2), c?=?10.251(2)Å, Z?=?4; 3: Orthorhombic, Pca2 _1, a?=?14.335(2), b?=?11.405(2), c?=?11.154(2)Å, Z?=?4 ). Both crystals consist of alternating complex cations [ML]²⁺ and anions [MnCl₄]^2? linked together by N–H···Cl–Mn and O–H···Cl–Mn hydrogen bonds forming 2D corrugated sheets in (2) and 1D helical chains in (3). Complex 2 represents the first single crystal structure elucidation of the complex containing L².     

Stereochemically active lone pairs of electrons in subvalent main fourth-group compounds. The crystal and molecular structures of {η5-C5H5Co[P(OC2H5)2O]3}2MII (M = Sn,Pb)

The air-stable, mixed main group-transition metal, trinuclear sandwich oxygen tripod 2/1 complexes, {η⁵-C₅H₅Co[P(OC₂H₅)₂O]₃}₂M, (1, M = Sn): C₃₄H₇₀Co₂O₁₈P₆Sn, a 18.871(12), b 22.461(12), c 12.671(7) Å, β 92.53(5)°, monoclinic space group P2₁/a, d_calc 1.472 g cm⁻³, Z = 4, R = 9.5%: 2 (M = Pb): C₃₄H₇₀Co₂O₁₈P₆Pb, a 18.787(8), b 22.397(9), c 12.674(3) Å, β 92,01(3)°, monoclinic space group P2₁/a, d_calc 1.594 gcm⁻³, Z = 4, R = 7.2%, have been subjected to single crystal X-ray analysis. Both complexes show a stereochemically active lone pair at the metal and coordination to two tridentate η⁵-C₅H₅Co[P(OC₂H₅)₂O]₃ groups. The angles through the MO₆ units are CoMCo 149.04(14)° and 150.96(7)° for M = Sn and Pb, respectively. The tilting of the two tripod ligand moieties is reflected in the MO internuclear distances which range from 2.24(3) to 2.83 (3) Å for M-Sn and 2.40 (2) to 2.66(3) Å for M = Pb, differences of 0.59(3) and 0.26(3) Å, respectively. The average distances are 2.48(3) and 2.51(2) Å for 1 and 2 which are isostructural.     

Study of direction of cyclization of malonodithioamides as a method of investigation of reactivity of α-diazothioacetamides

The reaction of malonothioamides with benzene-sulfonyl azide and 2-azido-3-ethylbenzthiazolium tetrafluoroborate gave amides of 2-diazothiomalonic acid, which underwent cyclization to a mixture of 5-N-R-amino-1,2,3-thiadiazole-4-carbothioamides and 5-amino-1,2,3-thiadiazole-4-N-R-carbothioamides. The ratio of the isomeric thiadiazoles formed in this reaction is the same as in the reactions of 2-diazo-2-cyanoacetamides, 5-amino-1,2,3-thiadiazole- and 5-mercapto-1,2,3-triazole-4-carboxamides with P₄S₁₀ and of 5-amino-1, 2,3-thiadiazole-4-carbonitriles with H₂S; it is characteristic of the influence of substituents on the reactivity of -diazothioacetamides. It was found that the cyclization of the diazo compounds is accelerated when electron-acceptor substituents are attached to the nitrogen atom of the carbothioamide group.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1106–1112, August, 1992.     

Quantum chemical studies of Lindqvist-type polyoxometalates containing late 3d transition metals ([(py)MIIW5O18]4? (M?=?Fe, Co, Ni)): MII�CN bonding and second-order nonlinear optical properties

The electronic and nonlinear optical (NLO) properties of Lindqvist-type tungstate containing late 3d transition metals [(py)MW₅O₁₈]^4? (M?=?Fe, Co, Ni) have been systematically investigated using density functional theory (DFT) method. The character of M?CN bond is analyzed using natural bond orbital methods. The first hyperpolarizabilities of [(py)MW₅O₁₈]^4? anions have been investigated by Coulomb-attenuating method (CAM-B3LYP). The NLO properties of [(py)MW₅O₁₈]^4? with different spin states are also studied. The results show that the static second-order polarizability (?? ₀) of [(py)⁵FeW₅O₁₈]^4? (Fe?=?quintet state) is 525.10?×?10^?30 esu, which is larger than those of [(py)⁴CoW₅O₁₈]^4? (?? ₀?=?120.72?×?10^?30 esu) and [(py)³NiW₅O₁₈]^4? (?? ₀?=?30.45?×?10^?30 esu) anions. Time-dependent DFT results reveal that the substituted transition metals-to-pyridine charge transfer may be responsible for the NLO properties of this kind of polyoxometalates.     

Synthesis of a Pair of Derivatives of N-Methylpyrrole Polyamide

A pair of derivatives of tetrameric N-methylpyrrole polyamide were synthesized in order to develop a new method for the study of interaction of the polyamide derivatives with DNA. Indole acetic acid and nicotinic acid were introduced to the polyamide in the synthesized compound, which showed an expected red shift in the UV spectrum. These compounds may function as a potential tool in the detection of the polyamide binding to DNA.     

Structure of Potassium of Undecatungstomononickelosilicate

ＳｔｒｕｃｔｕｒｅｏｆＰｏｔａｓｓｉｕｍｏｆＵｎｄｅｃａｔｕｎｇｓｔｏｍｏｎｏｎｉｃｋｅｌｏｓｉｌｉｃａｔｅＱｕＬｕｎ－Ｙｕ；ＭａＲｏｎｇ－Ｈｕａ；ＣｈｅｎＹａ－Ｇｕａｎｇ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉｓｔｒｙ，ＮｏｒｔｈｅａｓｔＮｏｒｍａｌＵ...     

Analysis of Significance of Unite Examination of AFP and DNA Polymorphism of P3 Promoter of IGF-ⅡGene

The DNA of P3 promoter region of IGF-Ⅱ gene was obtained by means of PCR technique. The examination of DNA polymorphism by restriction endonuclease BstE Ⅱ and the examination of AFP by bioluminescence immunoassay technique were carried out. The results have a significant difference(P<0.005). But the positive rate of AFP is higher than that of DNA polymorphism. The experimental result shows that the change of the DNA polymorphism of IGF-Ⅱis not the only carcinogenic factor. The suggested unite examination is the best method for the diagnosis of the primary hepatocellular carcinoma.     

Synthesis of Related Compounds of Carotenoid

类胡萝卜素是一类奇特的色素，由高等植物和微生物光化学合成，作为防止单线氧通过光敏反应产生危害的必要基团，类胡萝卜素最近受到了关注。类胡萝卜素联于富勒烯上，既可大大增加在可见光区域光诱导电子转移的有效吸收断面，又可抑制富勒烯敏化单线氧的危害能力。合成了类胡萝卜素的相关化合物，报道的某些反应条件先进且简洁。     

Analysis of Significance of Unite Examination of AFP and DNA Polymorphism of P3 Promoter of IGF- Ⅱ Gene

IntroductionTheinnatecharacterofthesolidcarcinomaistheresultthatcellgrowthgetsoutofcontrol.Itsbasicreasonconsistsintheabnormalityofthetumorgene .SomeonethinksthatthegeneofIGF Ⅱisoneofthecancergenesofthe primaryhepatocellularcarcino ma[1] ,andalsothinkstheoverexpressionofthegeneofIGF Ⅱtakesplaceintheearlierperiodofthepri maryhepatocellularcarcinoma ,whichmaybetheear lierdiagnosticnormofprimaryhepatocellularcarcino ma .ThefurtherresearcheshavedemonstratedthattheactivationofIGF Ⅱ genepromo…