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1.
Nucleophilic substitution of Pd(RaaiR′)Cl2 [RaaiR′=1-alkyl-2-(arylazo)imidazole, p-R—C6H4— N=N—C3H2NN-1-R′; where R= H(a)/Me(b)/Cl(c) and R′ = Et(1)/Bz(2)] with adenine (A) in MeCN–water (1:1) at 298 K, to form [Pd(A)2]Cl2, has been studied spectrophotometrically under pseudo-first-order conditions and the analyses support a nucleophilic association path. The reaction follows the rate law, rate = {a+k [A] 02[Pd(RaaiR′)Cl2]: first-order in Pd(RaaiR′)Cl2 and second-order in A. The rate increases as follows: Pd(RaaiEt)Cl2(1) < Pd(RaaiBz)Cl2(2) and Pd(MeaaiR′)Cl2(b) < Pd(HaaiR′)Cl2(a) < Pd(ClaaiR′)Cl2(c). External addition of Cl− (LiCl) suppresses the rate (rate 1/[Cl−]). The activation parameters,
H0 and
S0
of the reactions were calculated from the Eyring plot and support the proposed mechanism. 相似文献
2.
The reaction of [Pt(RaaiR′)(solvent)2]2+ with nucleobases (NB), adenine and guanine was studied and the products [Pt(RaaiR′)(NB)(H2O)](PF6)2RaaiR′ = 1-alkyl-2-(arylazo)imidazole, R′ = Me (1), Et (2); R = H (a),OMe (b), NO2(c)] characterized by i.r, u.v.–vis. and 1H-n.m.r spectroscopy. The solution spectra exhibit metal-to-ligand charge-transfer transitions (MLCT) and intra-ligand charge-transfer transitions. The position and symmetry of the bands depend on the nucleobase and arylazoimidazole. The coordination of the ligand is supported by 1H-n.m.r. spectral data. The redox property has been examined by cyclic voltammetric technique and shows the involvement of the azo group of the chelated ligand, RaaiR′ in the reduction process along with the irreversible reduction of the coordinated nucleobase. Binding with Bovine Serum Albumin (BSA) and Calf Thymus DNA was performed spectrophotometrically in the physiological buffer medium and spectral profile was recorded in 24 h. 相似文献
3.
L. B. Serezhkina E. V. Peresypkina A. V. Virovets I. V. Medrish D. V. Pushkin 《Russian Journal of Inorganic Chemistry》2009,54(10):1577-1580
Single crystals of Cs[(UO2)2(C2O4)2(OH)] · H2O were synthesized and structurally studied using X-ray diffraction. The compound crystallizes in monoclinic space group P21/m, Z = 2, with the unit cell parameters a = 5.5032(4) Å, b = 13.5577(8) Å, c = 9.5859(8) Å, β = 97.012(3)°, V = 709.86(9) Å3, R = 0.0444. The main building units of crystals are [(UO2)2(C2O4)2(OH)]? layers of the A2K 2 02 M2 (A = UO 2 2+ , K02 = C2O 4 2? , and M2 = OH?) crystal-chemical family. Uranium-containing layers are linked into a three-dimensional framework via electrostatic interactions with outer-sphere cations and hydrogen bonds with water molecules. 相似文献
4.
Triethylamine reacts with aqueous zinc acetate and the product of its thermolysis in the presence of benzoic acid to yield
the complexes [Zn7(μ4-O)(μ-OOCMe)10][η-OC(Me)OHNEt3]2 (1) and [Zn2(μOOCPh)4][η-OC(Me)OHNEt3]2 (2), respectively. The reactions of 1 and 2 with 3,5-dimethylpyrazole at room temperature in benzene yield pyrazolate-bridged binuclear complexes Zn2(μdmpz)2(Hdmpz)2(OOCR)2 (R = Me (3), Ph (4)). The structures of complexes 1–4 have been determined by X-ray crystallography. 相似文献
5.
Turan Kaya Yazıcılar Evrim Yılmaz Gürkan İbrahim Uçar Canan Kazak 《Transition Metal Chemistry》2009,34(6):669-676
Four novel transition metal benzenesulfonate (BS) complexes of imidazole (im) with a general formula [M(imH)3(H2O)3]·(BS)2 [M=Mn(II) (1), Ni(II) (2), Co(II) (3)] and [Cu(BS)(imH)3]·(BS) (4) have been synthesized and characterized by physicochemical and spectroscopic methods. The complexes 2 and 3 have also been characterized by single X-ray diffraction technique. The BS anion in complexes 1–3 acts as a counter anion, while in complex 4, it acts as both ligand and counter anion. The Ni and Co complexes are isomorphous, crystallizing in the monoclinic crystal
system with C2/c space group. Each metal(II) atom in 2 and 3 is octahedrally coordinated by three imidazole and three aqua ligands, adopting a mer-coordination mode with Ni(II) or Co(II) centers. In both 2 and 3, the H2C atom has bifurcated donor (O3 and O5) atoms, forming a bifurcated hydrogen bond. This hydrogen bond links the complex
cation and BS anion, forming one-dimensional hydrogen-bonded supramolecular chains. The complexes exhibit different decomposition
characteristics. Magnetic susceptibility measurement shows that complex 3 has orbital interactions. 相似文献
6.
E. A. Il’inchik T. M. Polyanskaya K. G. Myakishev 《Russian Journal of General Chemistry》2007,77(7):1148-1154
The structure of tri-μ2-disulfido-μ3-thiotris(diethyldithiocarbamato)-S,S′-triangle-trimolybdenum iodide [Mo3(μ3-S)(μ2-S2)3(Et2NCS2)3]I was determined. The compound was characterized by differential thermal analysis and IR, Raman, and X-ray electronic spectroscopy. 相似文献
7.
Abstract
Three novel lanthanide-organic frameworks: [Ln2(pyba)3(μ3-OH)2(μ2-OH)(H2O)] n (Ln = Er (1), Y (2), Dy (3) Hpyba = 4-pyridin-4-yl-benzoic acid) have been hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction. Structure analysis shows that each {Ln4(μ3-OH)4(μ2-OH)2} cluster units interconnect to form 1-D chains, which are further linked by π–π interactions to make a 3-D supramolecular network structure. Furthermore, the IR, PXRD and TGA of compounds 1–3 were also studied. 相似文献8.
N. G. Chernorukov O. V. Nipruk R. V. Abrazheev K. A. Chaplieva 《Russian Journal of General Chemistry》2016,86(9):1987-1990
An individual crystalline compound Pb(UO2)2O2(OH)2·(H2O) was obtained by reaction of synthetic schoepite UO3·2.25H2O with an aqueous solution of lead(II) nitrate under hydrothermal conditions. The composition and structure of this compound were determined, and the processes of its dehydration and thermal decomposition were studied by chemical analysis, X-ray diffraction, IR spectroscopy, and thermography. 相似文献
9.
S. P. Khranenko E. A. Shusharina S. A. Gromilov S. V. Korenev 《Journal of Structural Chemistry》2011,52(3):544-549
Crystal structures of two modifications of a binuclear Pd2(μ-ac)2(acac)2 complex are studied at 150 K and 297 K (ac = acetate; acac = acetylacetonate). It is demonstrated that in both cases, the packing of the complexes can be considered as pseudohexagonal, the molecules forming infinite chains by interactions between chelate rings with the shortest contacts Pd...C γ ~ 3.3 Å. 相似文献
10.
A. A. Pasynskii S. S. Shapovalov I. V. Skabitskii O. G. Tikhonova 《Russian Journal of Coordination Chemistry》2017,43(12):837-842
Syntheses and molecular structures of the heterometallic complexes of nickel cyclopentadienyl triphenylphosphine tellurophenolate with tungsten carbonyls (II and III) (CIF files CCDC nos. 1559733 and 1559734, respectively) are described. 相似文献
11.
Y. Ding D. S. Gao S. D. Li X. H. Li C. L. Li 《Russian Journal of Coordination Chemistry》2009,35(9):663-667
The title complex [Ni(Im)6](DBSH)2 · 2DMF(H2DBSH = 3,5-dibromosalicylaldehyde, Im = imidazole, DMF = N,N-dimethylformamide) has been prepared and characterized by X-ray diffraction analysis. It crystallizes in the monoclinic system, space group P21/c with a = 14.7271(13), b = 9.0221(8), c = 18.1143(16) Å, β = 100.408(2)°, V = 2367.2(4) Å3, Z = 2, M r = 1171.22, F(000) = 1172, ρ c = 1.643 g/cm3 and μ(MoK α) = 3.844 mm?1. The structure was refined to R = 0.0425 and wR = 0.1052 for 3646 observed reflections. The X-ray crystal structure analysis revealed that the center nickel(II) cation is bonded to six nitrogen atoms from six imidazole to form a six-coordinated elongated octahedron. The complex includes a DBSH2? anion and two DMF solvates. The intramolecular and intermolecular hydrogen bonds in the crystal structure play remarkably important role in the thermostability of the title complex. The electrochemical properties were studied in DMF with an electrochemical analyzer. 相似文献
12.
A novel Salen-type bisoxime ligand, 6,6′-dimethoxy-2,2′-[(1,4-butylene)dioxybis(nitrilomethylidyne)]diphenol (H2L) and its tetranuclear Cu(II) complex, [Cu4L2(pic)4(H2O)2]·2H2O, have been synthesized and characterized by elemental analyses, IR, TG-DTA and 1H-NMR etc. The X-ray crystal structure of the complex reveals that formation of a tetranuclear structure, which consists of four copper(II)
atoms, two pentadentate L2−units, four picratols, two coordinated water molecules and two crystallizing water molecules. Around four copper ions are
all octahedral geometries. It was demonstrated that the picratols in the tetranuclear copper(II) complex show a novel tridentate
coordination mode. 相似文献
13.
I. P. Malkerova A. S. Alikhanyan I. G. Fomina Zh. V. Dobrokhotova 《Russian Journal of Inorganic Chemistry》2010,55(1):53-55
Sublimation of europium pivalate binuclear complexes Eu2(Piv)6 and [Eu2(Piv)6 · (Phen)2] (Piv = (CH3)3CCOO, Phen = C12H8N2) in the temperature range of 383–660 K is studied by the Knudsen effusion method with mass-spectrometric analysis of the
gas phase. The vaporization of Eu2(Piv)6 is shown to be accompanied by polymerization and the formation of Eu2(Piv)6 and Eu4(Piv)12 molecules. The saturated vapor over the mixed-ligand complex of europium pivalate with o-phenanthroline consists of Phen, Eu2(Piv)6, and Eu4(Piv)12 molecules. The partial pressures of the gas components, as well as the standard enthalpies of sublimation and dissociation
of the reaction proceeding with removal of phenanthroline have been determined. 相似文献
14.
Ray L. Frost Sara J. Palmer Ross E. Pogson 《Journal of Thermal Analysis and Calorimetry》2012,107(3):905-909
Thermogravimetry combined with evolved gas mass spectrometry has been used to characterise the mineral crandallite CaAl3(PO4)2(OH)5·(H2O) and to ascertain the thermal stability of this ‘cave’ mineral. X-ray diffraction proves the presence of the mineral and
identifies the products of the thermal decomposition. The mineral crandallite is formed through the reaction of calcite with
bat guano. Thermal analysis shows that the mineral starts to decompose through dehydration at low temperatures at around 139 °C
and the dehydroxylation occurs over the temperature range 200–700 °C with loss of the OH units. The critical temperature for
OH loss is around 416 °C and above this temperature the mineral structure is altered. Some minor loss of carbonate impurity
occurs at 788 °C. This study shows the mineral is unstable above 139 °C. This temperature is well above the temperature in
the caves of 15 °C maximum. A chemical reaction for the synthesis of crandallite is offered and the mechanism for the thermal
decomposition is given. 相似文献
15.
G. B. Andreev M. Yu. Antipin N. A. Budantseva N. N. Krot 《Russian Journal of Coordination Chemistry》2005,31(11):800-803
A new neptunium(V) complex [(NpO2)2(CH3COO)2(H2O)] ? 2H2O was synthesized and its crystal structure was determined. The unit cell parameters are: a = 24.007(10) Å, b = 6.779(3) Å, c = 8.076(3) Å, space group Pnma, Z = 4, V = 1314.2(9) Å3, R = 0.049, wR(F2) = 0.105. The crystal structure of the compound is composed of neutral [(NpO2)2(CH3COO)2(H2O)] layers and molecules of the water of crystallization. Each of the crystallographically independent neptunoyl ions performs a bidentate function thus forming a composite system of cation-cation bonds. 相似文献
16.
A novel copper compound constructed from Wells-Dawson polyanion clusters and metal-organic complex subunits,[Cu(2,2′-Bipy)3]3(P2W18O62) · 2H2O(I), has been prepared under hydrothermal conditions, and characterized by elemental analysis, IR, UV, TG, cyclic voltammetry, and single-crystal X-ray diffraction. Crystal structural analysis indicates that I crystallizes in triclinic system, space group P \(\bar 1\), a = 15.6195(11), b = 17.144(2), c = 25.0900(15) Å, α = 93.1040(10)°, β = 94.309(3)°, γ = 102.642(2)°. Three Cu2+ ions have the same coordination environment: Cu(1), Cu(2), and Cu(3) are all six-coordinated by three 2, 2′-Bipy. The Dawson polyoxoanion [P2M18O62]6? do not coordinate with the Cu2+ ion added for charge balance. 相似文献
17.
S. P. Khranenko N. V. Kuratieva I. V. Korolkov S. A. Gromilov 《Journal of Structural Chemistry》2016,57(3):625-627
The structure of [Pb3(OH)4Co(NO2)3](NO3)(NO2)·2H2O is determined by single crystal X-ray diffraction. The crystallographic characteristics are as follows: a = 8.9414(4) Å, b = 14.5330(5) Å, c = 24.9383(9) Å, V = 3240.6(2) Å3, space group Pbca, Z = 8. The Co(III) atoms have a slightly distorted octahedral coordination formed by three nitrogen atoms belonging to nitro groups (Co–Nav is 1.91 Å) and three oxygen atoms belonging to hydroxyl groups (Co–Oav is 1.93 Å). The hydroxyl groups act as μ3-bridges between the metal atoms. The geometric characteristics are analyzed and the packing motif is determined. 相似文献
18.
D. V. Muratov A. S. Romanov P. V. Petrovskii M. Yu. Antipin A. R. Kudinov 《Russian Chemical Bulletin》2009,58(5):964-967
Cationic triple-decker complexes [CpCo(1,3-C3B2Me5)Ru(arene)]PF6 (arene is benzene (2a), p-cymene (2b)) with a bridging diborolyl ligand were synthesized by the reaction of the sand-wich anion [CpCo(1,3-C3B2Me5)]− (1) with [(arene)RuCl2]2. The structure of [2b]PF6 was confirmed by X-ray diffraction analysis. 相似文献
19.
E. V. Makotchenko E. A. Bykova E. Yu. Semitut Yu. V. Shubin P. V. Snytnikov P. E. Plyusnin 《Journal of Structural Chemistry》2011,52(5):924-929
The crystal structure of a double complex salt of the composition [Au(en)2]2[Cu(C2O4)2]3·8H2O (en = ethylenediamine) at 150 K is determined by single crystal X-ray diffraction. The crystal data for C20H48Au2Cu3N8O32 are: a = 9.1761(3) Å, b = 16.9749(6) Å, c = 13.4475(5) Å, β = 104.333(1)°, V = 2029.43(12) Å3, P21/c space group, Z = 2, d x = 2.450 g/cm3. It is demonstrated that the thermal decomposition of the double complex salt in a helium or hydrogen atmosphere affords the solid solution Au0.4Cu0.6. 相似文献
20.
E. V. Cherkasova E. V. Peresypkina A. V. Virovets T. G. Cherkasova 《Russian Journal of Inorganic Chemistry》2016,61(2):174-179
[Ln(H2O)8][Cr(NCS)6] · 5H2O aqua complexes, where Ln = Er (1), Lu (2), have been found in an aqueous solution instead of binary complex salts with an organic ligand in their cation, when crystal products of the reaction between Ln(NO3)3 · 6H2O (Ln = Er, Lu), K3[Cr(NCS)6] · 4H2O, and 8-oxyquinoline (C9H7NO) were studied by X-ray diffraction. Crystals of complexes 1 and 2 are isostructural and crystallize in triclinic system, space group P\(\bar 1\), Z = 2. For complex 1: a = 9.0677(4) Å, b = 9.3115(4) Å, c = 16.9595 Å, α = 81.526(2)°, β = 86.153(2)°, γ = 83.879(2)°, V = 1406.33(10) Å3, ρcalc = 1.894 g/cm3; for complex 2: a = 9.0438(3) Å, b = 9.2880(3) Å, c = 16.9181(3) Å, α = 81.7250(10)°, β = 86.1600(10)°, γ = 83.8850(10)°, V = 1396.38(7) Å3, ρcalc = 1.926 g/cm3. 相似文献