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1.
P. N. Bourosh M. D. Revenko E. F. Stratulat B. Wicher M. Gdaniec I. D. Korzha 《Russian Journal of Inorganic Chemistry》2014,59(6):545-557
Copper(II) salts were reacted with various quinoline aldehyde chalcogensemicarbazones to yield compounds formulated as Cu(HL)X2 · nH2O (I: HL = quinoline aldehyde thiosemicarbazone (HL1), X = ClO4, n = 2; II: HL = quinoline aldehyde 4-C2H5-thiosemicarbazone (HL1a), X = NO3, n = 0; III: HL = quinoline aldehyde semicarbazone (HL2), X = ClO4, n = 3 and IV: HL = quinoline aldehyde 4-Ph-semicarbazone (HL2a), X = NO3, n = 1). Regardless of the reagent ratio, the products were compounds having the metal: ligand ratio of 1: 1, where the organic ligand was coordinated tridentate in a molecular form. Single-crystal X-ray diffraction showed that, depending on the chalcogen atom in the organic ligand (S or O), the substituent in the 4th position (at the terminal nitrogen atom), and the specifics of the acido ligand, complexes I–IV had appreciably differing molecular structure organizations. The structures of I and III are formed by a 1D charged coordination polymer, ClO 4 ? anions, and water molecules and may be described by the formula [Cu(HL)(H2O)(ClO4)] n (ClO4) n · nH2O. Copper(II) coordination polyhedra in I and II are (4 + 2) and (4 + 1 + 1) tetragonal bipyramids, respectively. In II and IV, the structures are monomeric and can be described as [Cu(HL1a)(NO3)2] with the metal coordination polyhedron shaped as a (4 + 1) tetragonal pyramid in II and as [Cu(HL2a)(H2O)(NO3)](NO3) with the metal coordination polyhedron shaped as a (3 + 2) trigonal bipyramid in IV. The structure of II is built of molecular complexes, each comprising, apart from ligand HL1a, two monodentate coordinated NO 3 ? groups. The oxygen atom of one anion together with the NNS donor atom set of ligand HL1a form the base, and the oxygen atom of the other anion is in the apex of the coordination polyhedron. In IV, the structure is ionic and built of NO 3 ? anions and [Cu(HL2a)(H2O)(NO3)]+ complex cations, where a cationic coordination polyhedron has a trigonal-bipyramidal configuration with organic ligand HL2a positioned along the long edge. The bipyramidal base is made up by the oxygen atoms of the coordinated water molecule and monodentate nitrato group and the nitrogen atom N2 of the azomethyne group. 相似文献
2.
Rai A Sengupta SK Pandey OP 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(11-12):2761-2765
Ten new lanthanum(III) and praseodymium(III) complexes of the general formula Na[La(L)2H2O] (Ln=La(III) or Pr(III); LH2=thiosemicarbazones) derived from the condensation of isatin with 4-phenyl thiosemicarbazide, 4-(4-chlorophenyl) thiosemicarbazide, 4-(2-nitrophenyl) thiosemicarbazide, 4-(2-bromophenyl) thiosemicarbazide and 4-(2-methylphenyl) thiosemicarbazide, have been synthesized in methanol in presence of sodium hydroxide. The XRD spectra of the complexes were monitored to verify complex formation. The complexes have also been characterized by elemental analysis, molar conductance, electronic absorption and fluorescence, infrared, far infrared, 1H and 13C NMR spectral studies. Thermal studies of these complexes have been carried out in the temperature range 25-800 degrees C using TG, DTG and DTA techniques. All these complexes decompose gradually with the formation of Ln2O3 as the end product. The Judd-ofelt intensity parameter, oscillator strength, transition probability, stimulated emission cross section for different transitions of Pr3+ for 4-phenyl thiosemicarbazones have been calculated. 相似文献
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The Ligand Field Molecular Mechanics (LFMM) method has been applied to 85 Cu(II)-amine complexes, eighteen of which were selected to form a training set. A single set of parameters yields Cu-N bond lengths for four-, five- and six-coordinate systems generally within 0.04 A of their X-ray crystallographic values. Larger deviations are indicative of counterion effects and/or crystallographic artefacts arising from Jahn-Teller averaging. The LFMM treatment is flexible and unbiased and for simple ligands, automatically gives planar CuN(4) and tetragonally elongated CuN(6) complexes. In agreement with experiment, square-pyramidal coordination is marginally favoured over trigonal bipyramidal coordination for CuN(5) species. However, if the ligand requirements dictate, the LFMM accommodates trigonal bipyramidal coordination for CuN(5) species, tetrahedral distortions of CuN(4) species and cis-elongated CuN(6) species. 相似文献
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6.
Gerard A. van Albada Maarten G. van der Horst Simon J. Teat Patrick Gamez Olivier Roubeau Ilpo Mutikainen Urho Turpeinen Jan Reedijk 《Polyhedron》2009
In this study the synthesis, crystal structure and characterization of three new transition metal polynuclear compounds with formula [Cu(dipm)(μ-dca)2]n(H2O) (1), [Ni(dipm)(μ-dca)2]n(C2H6O)1/2 (2) and [Cd(dipm)(μ-dca)2]n (3) (in which dipm = bis(pyrimidin-2-yl)amine and dca = dicyanamide) are reported. The isostructural compounds 1 and 2 contain a double-bridging end-to-end dca unit connecting two metal ions and a single bridging end-to-end dca unit between subsequent metals. Compound 3 exhibits only single bridging end-to-end dca units, oriented in three directions, giving rise to a 3D framework. 相似文献
7.
Kretz T Bats JW Losi S Wolf B Lerner HW Lang M Zanello P Wagner M 《Dalton transactions (Cambridge, England : 2003)》2006,(41):4914-4921
Cationic dinuclear Cu(II) complexes 3 and 4 have been prepared using the novel hydroquinone-based imine chelators 2,5-((i)Pr(2)NCH(2)CH(2)N[double bond, length as m-dash]CH)(2)-1,4-(OH)(2)-C(6)H(2) (1) and 2,5-(pyCH(2)CH(2)N[double bond, length as m-dash]CH)(2)-1,4-(OH)(2)-C(6)H(2) (2), respectively (py = 2-pyridyl). X-Ray quality crystals of both complexes were grown from their DMF solutions. The sterically more encumbered compound crystallizes in the form of discrete dinuclear entities with Cu(II) centres in a distorted square-planar ligand environment (one coordination site is occupied by a DMF molecule). The pyridyl derivative 4 features dinuclear hydroquinone-bridged subunits similar to 3. However, the Cu(II) ions are now six-coordinate with two DMF molecules at an axial and an equatorial position of a Jahn-Teller-distorted octahedron. Moreover, the dinuclear subunits are no longer isolated but linked with each other via bridging hydroquinone oxygen atoms which occupy the second apical position of each octahedron. The structure suggests that the magnetic properties of the resulting coordination polymer of 4 could be described by a model valid for dimerized spin chains. As a result of this analysis the antiferromagnetic coupling constants J(1)/k(B) = 9.9 K (intradimer) and J(2)/k(B) = 0.9 K (interdimer) are obtained. Both in 3 and in 4, the hydroquinone --> semiquinone transition of the central bridging unit (E degrees ' = + 0.57 V, 3; E degrees ' = + 0.51 V, 4; DMF; vs. SCE) displays features of chemical reversibility. In the case of , reduction of Cu(II) centres requires a peak potential of E(p) = - 0.42 V. 相似文献
8.
Tarlok Singh Lobana Mani Kaushal Robin Bhatia Ritu Bala Ray J. Butcher Jerry P. Jasinksi 《Acta Crystallographica. Section C, Structural Chemistry》2022,78(1):30-35
In this investigation, the crystal structures of the thio-ligands 3-formylpyridine 4-phenylthiosemicarbazone (C13H12N4S, 1 ) and 4-benzoylpyridine 4-ethylthiosemicarbazone (C15H16N4S, 2 ), and of two new coordination compounds, chlorido(3-formylpyridine 4-phenylthiosemicarbazone-κS)bis(triphenylphosphane-κP)copper(I) acetonitrile monosolvate, [CuCl(C13H12N4S)(C18H15P)2]·CH3CN, 3 , and bis(3-formylpyridine 4-ethylthiosemicarbazonato-κ2N1,S)nickel(II), [Ni(C9H11N4S)2], 4 , are reported. In complex 3 , the thio-ligand coordinates in a neutral form to the Cu atom through its S-donor atom, and in complex 4 , the anionic thio-ligand chelates to the Ni atom through N- and S-donor atoms. The geometry of complex 3 is distorted tetrahedral [bond angles 99.70 (5)–123.23 (5)°], with the P—Cu—P bond angle being the largest, while that of complex 4 is square planar, with trans-S—Ni—S and N—Ni—N bond angles of 180°. 相似文献
9.
S. A. Malinovskaya P. V. Schastnev R. N. Musin V. N. Ikorsky 《Journal of Structural Chemistry》1993,34(3):398-401
The exchange Heisenberg interaction parameters have been determined from theoretical analysis of the temperature dependence of magnetic susceptibility of coordination cluster compounds [Cu(hfacac)2]3(Li(i))2 (hfacac is hexafluoroacetylacetonate, L(i) are 3-imidazoline nitroxides). Upon coordination of both N O oxygens and heterocycle N(3) atoms by Cu2+ ions, the interactions are ferromagnetic in nature and have the same order of magnitude. The minor intercluster interactions are antiferromagnetic.Institute of Chemical Kinetics and Combustion, Siberian Branch, Russian Academy of Sciences. International Tomography Center. Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii, Vol. 34, No. 3, pp. 70–74, May–June 1993.Translated by L. Smolina 相似文献
10.
Copper(II) coordination compounds with ferulic acid 总被引:1,自引:0,他引:1
The first two molecular structures of the ferulic acid (3-(4-hydroxy-3-methoxyphenyl)-2-propenoic acid, C10H10O4) coordination compounds are presented, namely, [Cu2(C10H9O4)4(CH3CN)2] 1 and [Cu2(C10H9O4)4(C6H6N2O)2]·4CH3CN (C6H6N2O = nicotinamide) 2. Both compounds were synthesised from the starting mixture of Cu2O and CuCl upon copper oxidation in the acetonitrile solution. The single-crystal X-ray diffraction analysis of 1 and 2 reveals the binuclear structure of the ‘paddle–wheel’ type for both complexes. 1 and 2 are unstable outside mother liquid due to loosely bound acetonitrile molecules. The final products of decomposition are [Cu2(C10H9O4)4] 1a and [Cu2(C10H9O4)4(C6H6N2O)2] 2a, which were characterized by several physico-chemical methods. The triplet X-band EPR spectra of 1a and 2a, showing signals BZ1 15 mT, B2 460 mT and BZ2 580 mT, are in agreement with the expected data for the binuclear tetracarboxylate units, found in the structures of the parent complexes 1 and 2. Together with the room temperature magnetic susceptibility data, μeff/B.M. 1.40 (1a), 1.48 (2a), the EPR spectra analysis confirm the antiferromagnetic interaction in 1a and 2a. This is suggesting preservation and stability of the paddle–wheel structures in 1a and 2a. 相似文献
11.
Several new 1D coordination polymers have been synthesised using the anionic ligand carbamoyldicyanomethanide, C(CN)2(CONH2)− (cdm). The polymeric complexes [Cu(cdm)2(py)2]·2MeOH (1), [Cu(cdm)2(4-Etpy)2]·2MeOH (2), [Cu(cdm)2(3,5-Me2pzH)2]·2MeOH (3) and [Cu(cdm)2(3-HOCH2py)2]·2MeOH (4) (py = pyridine; 3,5-Me2pzH = 3,5-dimethylpyrazole) contain Cu(II) atoms bridged by μ2-(N,N′) cdm ligands between equatorial and axial coordination sites. The use of monodentate co-ligands brings about polymeric products, in contrast to the use previously of chelating co-ligands which facilitate the formation of discrete products. These 1D polymeric complexes are connected by hydrogen bonding between the amide functionalities and the lattice solvent. In the structures of 3 and 4 the neutral ligands also contain hydrogen bond donor groups that supplement the amide ring motif. Two other complexes have been obtained that are polymeric chains of alkoxide-bridged Cu(II) dimers. The complexes [Cu(cdm)(MeO)(2-amp)] (5) and [Cu(cdm)(dmap)] (6) (2-amp = 2-(aminomethyl)pyridine and dmap = dimethylaminopropoxide) are remarkably similar despite the different ligands that they contain. Bridging between dimers is via μ2-(N,O) cdm ligands, consequently altering the nature of the hydrogen bonding between adjacent chains compared to the simple polymeric species 1–3. 相似文献
12.
Henryk J. Zawadzki 《Transition Metal Chemistry》1996,21(6):481-486
Summary New coordination compounds of NiII and CoII with dichloropyrimidinoguanidine (L) have been obtained and characterized by physico-chemical and spectroscopic methods. The complexes have the general formulae: [ML3](ClO4)2, [ML2(SO4)], [ML2(NCS)2], (M = Ni or Co), [NiL2(ClO4)2] and [CoL2](ClO4)2. The ligands are bonded to the metal ion via one nitrogen atom from the pyrimidine heterocyclic ring and one from the guanidine group. 相似文献
13.
Cu(II)-脱乙酰壳聚糖配位聚合物的配位数 总被引:3,自引:0,他引:3
IR,ESR和XPS的测试结果表明,脱乙酰壳聚糖(简记CS)膜在铜氨水溶液浸渍过程中Cu(II)既与CS发生配位反应形成Cu(II)-CS配位聚合物,也产生吸附作用。ESR谱示出CuCl~2.2H~2O与Cu(II)-CS膜中的Cu(II)均含有一个单电子,可以利用XPS的Shake-up效应研究Cu(II)-CS配位聚合物的配位数,所得结果为4。又以同样的方法研究Cu(II)-聚乙烯醇(简记PVA)配位聚合物的配位数,发现Cu(II)是以低自旋状态的dsp^2杂化空轨道与PVA的羟基氧配位,其配位数也是4,这与资料所报道的一致,从而间接地验证了此方法研究Cu(II)-CS配位聚合物配位数的可靠性。 相似文献
14.
Rhenium(V) coordination compounds with pyroracemic acid and phenylglyoxylic acid thiosemicarbazones were synthesized for various metal-to-ligand ratios in 1–7 M hydrohalic acids. The composition and structure of the complexes were characterized using a set of physicochemical methods. The thermal stability of rhenium(V) complexes with pyroracemic acid and phenylglyoxylic acid thiosemicarbazones and rhenium(V) solvato complexes with pyroracemic acid thiosemicarbazone was studied thermogravimetrically. The thermolysis mechanism for the complexes was determined as follows: elimination of outer-sphere water, decarboxylation, and dehalogenation. 相似文献
15.
El-Asmy AA Al-Hazmi GA 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2009,71(5):1885-1890
The ligational behavior of 2-hydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone N-substituted thiosemicarbazones towards Ni(II) and Cu(II) ions has been investigated. The isolated complexes were identified by elemental analyses, molar conductance, magnetic moment, IR, UV-vis and ESR spectral studies. The IR spectra indicated that the investigated thiosemicarbazones lost the N(2) proton or the N(2) and OH protons and act as mononegative or binegative tridentate ligands. The ligands containing methoxy group facilitate the deprotonation of OH by resonance more than the SH. Most of the Ni(II) complexes measured subnormal magnetic moments due to square-planar+tetrahedral configuration and supported by the electronic spectra. The percentage of square-planar to tetrahedral was calculated and found in agreement with the ligand splitting energy (10Dq). Also, Cu(II) complexes measured subnormal values due to the interaction between copper centers; the lower the value the higher the interaction. It was found that the substitutent has a noticeable effect on the distortion of the complex. The ESR spectra of some solid Cu(II) complexes at room temperature exhibit g(parallel)>g( perpendicular)>2.0023 confirming a square-planar structure. 相似文献
16.
《Journal of Coordination Chemistry》2012,65(5):453-460
Two malonato-bridged hexamethylenetetramine coordination polymers, M2(hmt)(H2O)2(mal)2 [hmt?=?hexamethylenetetramine, mal?=?malonate(2-), M?=?Mn (1), Cu (2)] were prepared and structurally characterized. The isostructural complexes are orthorhombic, space group Imm2, with a?=?7.104(1), b?=?15.982(3), c?=?7.702(1)?Å, Z?=?2, D calc?=?1.862?g?cm?3(1) and a?=?6.962(3), b?=?15.500(7), c?=?7.627(3)?Å, Z?=?2, D calc?=?2.047?g?cm?3for 2. The transition metals are octahedrally coordinated by one nitrogen atom of an hmt ligand and five oxygen atoms of a water molecule and three malonate anions. The latter coordinate in chelating/bis-monodentate mode to give 2D layers with a (4,?4) topology, and which are pillared by bridging bidentate hmt ligands to generate an open 3D framework with channels extending in the [001] direction. Over the temperature range 5–300?K, 2 behaves paramagnetically, following the Curie–Weiss law χm(T???θ)?=?4.521(6)?cm3mol?1K with a Weiss constant θ?=??4.8(2)?K. 相似文献
17.
Iu. Shatrava V. Ovchynnikov K. Gubina S. Shishkina O. Shishkin V. Amirkhanov 《Structural chemistry》2016,27(5):1413-1425
A series of new 3d metal complexes based on dimethyl pyridin-2-ylcarbamoylphosphoramidate (HL) was synthesized. The compounds with general formula M(HL)2Cl2·nH2O and M(L)2·nH2O (M=Co2+, Cu2+, Ni2+) were characterized by means of single-crystal X-ray analysis and IR spectroscopy. The organic ligands in all complexes are coordinated via oxygen atom of the carbonyl group and nitrogen atom of the heterocycle. The coordination environment of the central atoms is a distorted octahedron. The axial positions in the Co(II) and Ni(II) complexes with deprotonated ligands are occupied by water molecules. The Co(II) and Cu(II) complexes with phosphoryl ligands in a neutral form have different ligands in the axial positions: in the Co(II) complex, the positions are occupied by two water molecules, whereas in the Cu(II) complex, the positions are occupied by two chlorine anions. The structure of HL was experimentally and theoretically obtained by utilizing single-crystal X-ray analysis and DFT calculations. The computationally optimized geometric parameters for HL show a good agreement with the experimental results. 相似文献
18.
S. S. Budnikov S. V. Donu L. F. Chapurina I. B. Bersuker I. A. D'yakon 《Theoretical and Experimental Chemistry》1985,21(3):335-340
The MWH method has been used in calculations on the electronic structures of compounds of copper(II) with -amino-acids CuGLY(L-Ser), Cu(L-Alan)(L-Ser), CuGly2·H2O, as well as for the free amino-acids: alanine, glycine, and serine. The proper energies and eigenvectors have been derived together with the charges on the atoms, which indicate the mode of coordination in these systems with DNA fragments involving the formation of sandwich complexes, and this provides a qualitative explanation of the differences in antitumor activity between these compounds.Translated, from Teoreticheskaya i'Éksperimental'naya; Khimiya, No. 3, pp. 351–356, May–June, 1985. 相似文献
19.
Barta Holló Berta Vojinović Ješić Ljiljana S. Radanović Mirjana M. Rodić Marko V. Jaćimović Željko K. Mészáros Szécsényi Katalin 《Journal of Thermal Analysis and Calorimetry》2020,139(1):451-473
Journal of Thermal Analysis and Calorimetry - The thermodynamic and economic analysis of a transcritical carbon dioxide power cycle is coupled with solar thermal subsystem and LNG subsystem. Solar... 相似文献
20.
The structure of CuII complexes with hydroxamic acids Cu[R1N(O)−(O)CR2]2, where R1=Ph, R2=Me; R1=Me, R2=Ph, was studied by ESR spectroscopy. In toluene solutions and low-temperature glasses, the complexes exist as two forms,
which were identified ascis-andtrans-isomers. The proportions of the isomers were determined.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 726–729, April, 1999. 相似文献