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1.
Two new dicyanamide coordination polymers, {Mn(dmpz)[N(CN)2]2}2 (1) and {Cu(dmpz)[N(CN)2]2}2 (2)(dmpz=3,5-dimethylpyrazole), were synthesized and characterized by single crystal X-ray diffraction analysis and IR spectroscopy. In 1 and 2 the metal ions have two different coordination modes, where one is coordinated to four dicyanamide anions and two monodentate dmpz molecules to form a slightly distorted octahedral geometry, while the other adopts octahedral geometry, surrounded by four nitrile N atoms and two amide N atoms of the dicyanamide anions. Both complexes contain two alternating chains that are parallel to each other. 相似文献
2.
Anionie Nickel Pseudohalide Complexes of the Types [Ni{N(CN)2}3]? and [Ni{N(CN)2}2(NCS)2]2? The preparation of a new type of anionic pseudohalide complexes of nickel [Ni{N(CN)2}3]? and of mixed thiocyanate-dicyanamide complexes [Ni{N(CN)2}2(NCS)2]2? is reported. The structures of the complexes are discussed on the basis of IR- and magnetic measurements. The new compounds are representing polymer octahedral complexes with a bridging function of the dicyanamide ligands. 相似文献
3.
Jerzy Mroziński Jiří Kohout Mária Hvastijová Helmut Köhler 《Transition Metal Chemistry》1986,11(12):481-484
Summary New coligand isomers of composition Cu{N(CN)2}2(pz)2 and Cu{pz · N(CN)2}2 (pz = pyrazole) were prepared and studied by measuring their magnetic susceptibilities up to 4.2K and by aid of their e.s.r., ligand field and i.r. spectra. The susceptibility data have been analysed with various models for the exchange-coupled copper(II) polymers. It is shown that the resultant exchange coupling is ferromagnetic for Cu{N(CN)2}2(pz)2 (J 1.1 - 1.4 cm–1) but antiferromagnetic for Cu{pz · N(CN)2}2 (J –0.4 cm–1). A polymeric chain structure is proposed for Cu{N(CN)2}2(pz)2 havingpseudo-octahedrally coordinated copper(II) and CN-bridging dicyanamide ligands. Its coligand isomer contains anionic chelate ligands, formed by nucleophilic addition between N(CN)2 and pz in the copper(II) coordination sphere, and giving with this central atom a square-planar system. Definite, but slight axial interaction takes place between these structure units. 相似文献
4.
Meng ZS Guo FS Liu JL Leng JD Tong ML 《Dalton transactions (Cambridge, England : 2003)》2012,41(8):2320-2329
The syntheses, structural determinations and magnetic studies of tetranuclear M(II)Ln(III) complexes (M = Ni, Zn; Ln = Y, Gd, Dy) involving an in situ compartmentalized schiff base ligand HL derived from the condensation of o-vanillin and 2-hydrazinopyridine as main ligand are described. Single-crystal X-ray diffraction reveals that all complexes are closely isostructural, with the central core composed of distorted {M(2)Ln(2)O(4)} cubes of the formulas [Ni(2)Ln(2)(μ(3)-OH)(2)(L)(2)(OAc)(4)(H(2)O)(3.5)](ClO(4))(2)·3H(2)O (Ln = Y 1 and Gd 2), [Ni(2)Dy(2)(μ(3)-OH)(2)(L)(2)(OAc)(5)(EtOH)(H(2)O)(1.5)](ClO(4))·EtOH·H(2)O (3) and [Zn(2)Ln(2)(μ(3)-OH)(2)(L)(2)(OAc)(5)(EtOH)(H(2)O)](ClO(4))·2EtOH·1.5H(2)O (Gd 4 and Dy 5). The Ln(III) ions are linked by two hydroxo bridges and each M(II) ion is also involved in a double phenoxo-hydroxo bridge with the two Ln(III) ions, so that each hydroxo group is triply linked to the two Ln(III) and one M(II) ions. The magnetic properties of all complexes have been investigated. Ni(2)Y(2) (1) has a ferromagnetic Ni(II)Ni(II) interaction. A weak ferromagnetic Ni(II)Ln(III) interaction is observed in the Ni(2)Ln(2) complexes (Ln = Gd 2, Dy 3), along with a weak antiferromagnetic Ln(III)Ln(III) interaction, a D zero-field splitting term for the nickel ion and a ferromagnetic Ni(II)Ni(II) interaction. The isomorphous Zn(2)Ln(2) (Ln = Gd 4, Dy 5) does confirm the presence of a weak antiferromagnetic Ln(III)Ln(III) interaction. The Ni(2)Dy(2) complex (3) does not behave as a SMM, which could result from a subtractive combination of the Dy and Ni anisotropies and an increased transverse anisotropy, leading to large tunnel splittings and quantum tunneling of magnetization. On the other hand, Zn(2)Dy(2) (5) exhibits a possible SMM behavior, where its slow relaxation of magnetization is probably attributed to the presence of the anisotropic Dy(III) ions. 相似文献
5.
Attila Kovács 《International journal of quantum chemistry》2020,120(1):e26051
Lanthanide dinitrogen complexes, Ln(N2) x (x = 1-8), were investigated by Density Functional Theory computations using the B3LYP exchange-correlation functional in conjunction with quasirelativistic pseudopotentials for Ln. After a recent study on the lanthanum complexes (A. Kovács, Structural Chemistry 2018 , 29, 1825), the present study aimed to probe the changes upon variously filled 4f subshells of Ln on the structures, stabilities, and bonding properties in related complexes of Nd, Ho, and Lu. The bonding properties were assessed on the basis of natural atomic charges, Ln valence orbital populations, and analysis of bonding molecular orbitals. 相似文献
6.
J. Cernák J. Skorsepa J. Chomic I. Potocnák J. Hoppan 《Journal of Thermal Analysis and Calorimetry》1994,41(1):91-98
Two new tetracyano complexes of the composition MnenNi(CN)4 and MnenCd(CN)4 were prepared and identified. Their struture and properties were investigated by IR and UV-VIS spectroscopy, X-ray powder diffraction and by measuring magnetic moments. The results were confronted with the structure and properties of the compounds CdenNi(CN)4 and CdenCd(CN)4. The results of this study show a considerable similarity between these groups of compounds. The thermal behaviour of all the examined compounds was investigated derivatographically. The following order of thermal stability of the investigated complexes was observed: Cd?Cd(215°C)相似文献
7.
Icbudak H. Heren Z. Kose D. Ali Necefoglu H. 《Journal of Thermal Analysis and Calorimetry》2004,76(3):837-851
The mixed-ligand p-hydroxybenzoate complexes of Ni(II), Cu(II) and Zn(II) with nicotinamide and N,N-diethylnicotinamide were synthesized and
characterized by elemental analysis, magnetic susceptibility measurements and mass spectrometry. The thermal behavior of the
complexes was studied by simultaneous TG, DTG and DTA methods in static air atmosphere. The infrared spectral characteristics
of the complexes are also discussed. The complexes contain two water molecules, two p-hydroxybenzoato (p-hba) and two nicotinamide (na) (or diethylnicotinamide (dena)) ligands per formula unit. In these complexes,
all ligands are coordinated to the metal ion as monodendate ligands. In Zn(II)-na and Cu(II)-dena complexes, thep-hydroxybenzoate behaves as bidentate chelating ligand through carboxylic oxygen atoms. The decomposition pathways and the
stability of the complexes are interpreted in the terms of the structural data. The final decomposition products were found
to be the respective metal oxides.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
8.
Four air- and moisture-stable new palladium(II) complexes 2a–2c and 4 have been synthesized from easily available 2-arylnaphthoxazole derivatives. The detailed structures of 2c and 4 have been determined by single-crystal X-ray analysis. The Pd–N, Pd–C bonds in palladacycle complexes 2a–2c and the Pd–N, Pd–O bonds in complex 4 form the basis for five- and six-membered chelate rings, respectively. These complexes were applied as efficient phosphine-free catalysts for Heck reactions with aryl bromides and ethyl acrylate. Typically, in the presence of two equivalent n-Bu4NBr, using 0.01% of palladacycle complex 2c as catalyst and two equivalent of K2CO3 as base in DMF at 140 °C provided coupled products in moderate to high yields. 相似文献
9.
E. Jóna A. Mašlejová M. Kubranová P. Šimon 《Journal of Thermal Analysis and Calorimetry》1996,46(1):129-138
The stoichiometry of thermal decomposition and the relationship between the thermal parameters (quasi-equilibrium decomposition temperaturesT
D and decomposition entalpies H
D) of NiL4(NCS)2 complexes (L=imidazole derivatives) were studied. It was found that changes in the experimental conditions strongly influence the decomposition stoichiometry. TheT
D and H
D can be ordered in the following sequence (according toL): imidazole<2-Me imidazole<2-Et imidazole相似文献
10.
11.
12.
The [Co(HOr)(H2O)2(im)2] (1), [Ni(HOr)(H2O)2(im)2] (2), [Zn(H2O)2(im)4](H2Or)2 (3) and [Cd(HOr)(H2O)(im)3] (4) complexes (H3Or: orotic acid, im: imidazole) were synthesized and characterized by elemental analysis, magnetic and conductance measurements,
UV-vis and IR spectra. The thermal behaviour of the complexes was also studied by simultaneous thermal analysis techniques
(TG, DTG and DTA). The orotate ligand (HOr2−) coordinated to the Co(II), Ni(II) and Cd(II) ions are chelated to the deprotonated pyrimidine nitrogen (N(3)) and the carboxylate oxygen, while do not coordinate to the Zn(II) ion is present as a counter-ion (H2Or−). The first thermal decomposition process of all the complexes is endothermic deaquation. This stage is followed by partially
(or completely) decomposition of the imidazole and orotate ligands. In the later stage, the remained organic residue exothermically
burns. On the basis of the first DTGmax, the thermal stability of the complexes follows order: 2, 176°C>1, 162°C>4, 155°C>3, 117°C in static air atmosphere. The final decomposition products which identified by IR spectroscopy were the corresponding
metal oxides. 相似文献
13.
Sugita M Yamaguchi A Yamagiwa N Handa S Matsunaga S Shibasaki M 《Organic letters》2005,7(23):5339-5342
[reaction, structure: see text] Chiral Y{N(SiMe3)2}3/linked-BINOL catalyst generated Y-enolate in situ from various hydroxyketones (R2 = aryl, heteroaryl). Beta-amino-alpha-hydroxy ketones (R1 = aryl, heteroaryl, alkenyl) were obtained syn-selectively (up to 96/4) in high ee (up to 98%) and good yield (up to 98% yield). 相似文献
14.
A combined solid and solution phase methodology for the synthesis of a series of mononuclear and polynuclear zinc benzoate complexes is described. The substituent on the aromatic ring and the effect of solvent on deciding the composition of the complexes is presented. From the 4-substituted benzoic acids 4-methylbenzoic acid (ptolH), 4-nitrobenzoic acid (pnitrobenH) and 4-chlorobenzoic acid (pchlorbenH), the mononuclear complexes [Zn(ptol)2(H2O)2], [Zn(pnitroben)2(H2O)(DMSO)2] and [Zn(pchlorben)2py)2] (where DMSO = dimethylsulfoxide, py = pyridine) have been synthesized and structurally characterised. Zinc complexes from the reaction of zinc sulfate heptahydrate with 3-methylbenzoic acid (mtolH) and 2-methylbenzoic acid (otolH), the dinuclear complexes [Zn2(μ2-mtol)4(py)2], [Zn2(μ2-otol)4(py)2], pentanuclear complex [Zn5(μ2-mtol)6(mtol)2(μ3-OH)2 (py)2] and tetranuclear complex [Zn4(μ2-otol)6(μ4-O) (DMSO)2], have been prepared by varying the reaction conditions and the complexes have been structurally characterized. 相似文献
15.
Zhang SH Li N Ge CM Feng C Ma LF 《Dalton transactions (Cambridge, England : 2003)》2011,40(12):3000-3007
Three polynuclear complexes, [NiNa(μ(1,1,1)-N(3))(μ-hmb)(2)(DMF)](2), (1), [Ni(4)(μ(3)-OMe)(4)(heb)(4)(MeOH)(1.05)(H(2)O)(2.95)], (2) and [Ni(III)(OH)(6)(hmb)(6)Ni(II)(6)]·(ClO(4))(3) (3) (Hhmb = 2-hydroxy-3-methoxy-benzaldehyde; Hheb = 2-hydroxy-3-ethoxy-benzaldehyde), were prepared by reaction of the appropriate ligand with nickel(II) perchloride hexahydrate under solvothermal conditions. All compounds were characterized by elemental analysis, IR spectroscopy and X-ray single-crystal diffraction. Compound 1 exhibits a centrosymmetric heterotetranuclear cluster which represents the first nickel complex to possess two connected face-sharing cubes structure {Ni(2)Na(2)N(2)O(4)}. Compound 2 has a tetranuclear Ni cluster with a cubane topology in which the Ni(II) and the oxygen atoms from the methanol ligands occupying alternate vertices of the cube. Compound 3 consisits of a mixed-valence [Ni(III)(OH)(6)(hmb)(6)Ni(II)(6)](3+) subunits and it represents the first nickel {Ni(II)(6)Ni(III)} complex to possess a planar hexagonal disc-like structure. The results show that the minor ligand modifications or solvent change have a key role in the structural control of the self-assembly process. Magnetic properties of 1-3 in the 300-2 K have been discussed. The {Ni(2)Na(2)} (1) and {Ni(4)} (2) core display dominant ferromagnetic interactions from the nature of the binding modes through μ(3)-N(3)(-) or μ(3)-OCH(3)(-), while {Ni(II)(6)Ni(III)} core (3) displays dominant anti-ferromagnetic interactions from the nature of the binding modes through μ(3)-OH(-). 相似文献
16.
The thermal stabilities of 5-chloro-2-methoxybenzoates of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) were studied in air and
nitrogen atmospheres. The complexes were obtained as mono-, di-, tetra-and pentahydrates with a metal to ligand ratio of 1:2
and with colours typical for M2+ ions (Mn-slightly pink, Co-pink, Ni-green, Cu-blue and Zn-white) and as polycrystalline compounds. When heated they dehydrate
to form anhydrous salts which nextare decomposed to the oxides of the respective metals in air while in nitrogen to the mixtures
of metal oxides and oxychlorides and carbon. The most thermally stable in air, nitrogen and argon atmospheres is 5-chloro-2-methoxybenzoate
of Cu(II) while the least thermally stable is that of Co(II).
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
17.
Pseudohalogen Compounds. Synthesis and Reactivity of Alkyl- and Arylammonium Dicyanamides, Tricyanmethanides, and Dicyanmethanidoacetates [RNH3]X (X ? N(CN)2, C(CN)3, C(CN)2C(O)CH3) The syntheses of alkyl- and arylammonium dicyanamides, tricyanmethanido, and dicyanmethanido-acetates are reported. At higher temperatures the synthesized dicyanamides and tricyanmethanides are reacting to the corresponding cyanoguanidine and to 1,1-diamino-2,2-dicyano-ethene derivatives, respectively. The new compounds are characterized on the basis of their i.r. spectra and elemental analyses. 相似文献
18.
L’. Lajdová E. Jóna S. Šnircová J. Miklovič P. Segl’a M. Pajtášová D. Ondrušová S. C. Mojumdar 《Journal of Thermal Analysis and Calorimetry》2009,96(1):59-62
The stoichiometry of thermal decomposition of the complexes Ni(NCS)2(fpy)4 (I), Ni(NCS)2(bfpy)4 (II) and Ni(NCS)2(CF3Phfpy)4 (III) (where fpy=furopyridine, bfpy=benzo-[2,3]furo[3,2-c]pyridine, CF3Phfpy=2-(3-fluoromethylphenyl) furo[3,2-c]pyridine) have been investigated in nitrogen atmosphere from room temperature to
500°C by means of TG and DTG. The results revealed that release of the heterocyclic ligands occurs in two steps. IR data suggested
that fpy, bfpy and CF3Phfpy ligands were coordinated to Ni(II) through the N atom of the respective heterocyclic rings and same is the case with
the anionic NCS group. 相似文献
19.
Sevim Akyüz 《Journal of inclusion phenomena and macrocyclic chemistry》1985,3(4):403-407
The results of an infrared and Raman spectroscopic study are reported for two new metal 2-methylpyridine tetracyanonickelate complexes, M(C6H7N)2Ni(CN)4, M=Ni or Cd. Their structure consists of corrugated polymeric layers of {M-Ni(CN)4} with 2-methylpyridine molecules bound directly to the metal (M). These complexes can act as host lattices in the formation of inclusion compounds with dioxane guest molecules. 相似文献
20.
Wolfgang Hiller Stephanie Frey Joachim Strähle Gernot Boche Wolfgang Zarges Klaus Harms Michael Marsch RenéA Wollert Kurt Dehnicke 《欧洲无机化学杂志》1992,125(1):87-92
The Crystal Structures of {Li3(12-crown-4)2[HC(CN)2]3}, {Na(15-crown-5)[HC(CN)2]}, and {NaN(nBu)4[HC(CN)2]2 · THF} The preparation and the crystal structures of the title compounds 1 — 3 are described. 1 forms a polymeric chain structure, in which one of the lithium ions is linked by Li…NCC(H)CN… bridges. The remaining lithium ions form (12-crown-4)Li[NCC(H)CN] units, which are coordinated by one of the nitrogen atoms of the dicyanomethanide ions with the lithium ions of the chain. 2 forms an ion pair, in which the sodium ion is coordinated by the five oxygen atoms of the crown ether molecule and by one nitrogen atom of the dicyanomethanide ion. 3 has a threedimensional network, in which the sodium ions are coordinated in a distorted tetrahedral manner by the nitrogen atoms of the dicyanomethanide ions. In the cavities of the network the tetrabutylammonium ions and the THF molecules are found. 相似文献