Über Synthesen der Verbindungen von Mn,Fe, Co,Ni, Cu und Zn mit Hydrazidokohlensäure

Zusammenfassung Die Synthesen und einige Eigenschaften der Verbindungen von zweiwertigem Mn, Cu, Fe, Co, Ni und Zn mit Hydrazidokohlensäure werden beschrieben. Die Verbindungen von Fe, Co, Ni und Zn sind Hydrazinium-hydrazidocarbonato-metallate(II) der allgemeinen Formel N₂H₅[Me ^II(N₂H₃COO)₃]·H₂O, die von Mn und Cu sind aber einfache Hydrazido-carbonate der FormelMe ^II(N₂H₃COO)₂·n H₂O. Die Ergebnisse magnetochemischer Messungen sowie der orientierender Messungen der thermischen Eigenschaften werden angegeben.

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The syntheses and some properties of the compounds of bivalent Mn, Fe, Co, Ni, Cu and Zn with hydrazido-carbonic acid are described. The compounds of Fe, Co, Ni and Zn are hydrazinium hydrazido-carbonato-metallates(II) with the formula N₂H₅[Me ^II(N₂H₃COO)₃]·H₂O. The compounds of Mn and Cu are hydrazido-carbonatesMe ^II(N₂H₃COO)₂·n H₂O. The results of magnetic and preliminary measurements of thermal properties are given.

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J. Slivnik, A. malc, B. Sedej undM. Vilhar, Vestnik SKD (Bull. Soc. chim. Slovène)11, 53 (1964).     

MC_2O_4(M=Mn、Fe、Co、Ni、Cu、Zn)的热力学及其热分析动力学

用DSC、TGA技术分别在N2气氛和O2气氛下对MC2O4(M=Mn、Fe、Co、Ni、Cu、Zn)的脱水和分解过程作了热力学和动力学的研究.在N2气氛下,MC2O4·2H2O(M=Mn、Fe、Co、Ni、Zn)脱水温度Tde和脱水焓!deHm随原子序数Zre递增呈现明显的“二分组效应”;!deHm在(96.46±7.00)kJ·mol-1范围内波动;MC2O4·2H2O(M=Mn、Fe、Ni)的分解温度Td随原子序数递增呈现良好的线性关系;且各草酸盐分解得到氧化物(CuC2O4生成Cu、CuO混合物)时,MC2O4(M=Co、Ni、Cu)分解焓随原子序数增大也存在良好的线性关系.各草酸盐除NiC2O4·2H2O脱水过程和FeC2O4分解过程外,其余各过程机理函数均为随机成核和随后成长型.     

MC2O4(M=Mn、Fe、Co、Ni、Cu、Zn)的热力学及其热分析动力学

用DSC、TGA技术分别在N₂气氛和O₂气氛下对MC₂O₄(M=Mn、Fe、Co、Ni、Cu、Zn)的脱水和分解过程作了热力学和动力学的研究. 在N₂气氛下, MC₂O₄•2H₂O(M=Mn、Fe、Co、Ni、Zn)脱水温度Tde和脱水焓ΔdeHm随原子序数Zre递增呈现明显的“二分组效应”；ΔdeHm在(96.46±7.00) kJ•mol^-1范围内波动；MC₂O₄•2H₂O (M=Mn、Fe、Ni)的分解温度Td随原子序数递增呈现良好的线性关系；且各草酸盐分解得到氧化物(CuC₂O₄生成Cu、CuO混合物)时, MC₂O₄(M=Co、Ni、Cu) 分解焓随原子序数增大也存在良好的线性关系. 各草酸盐除NiC₂O₄•2H₂O脱水过程和FeC₂O₄分解过程外, 其余各过程机理函数均为随机成核和随后成长型.     

Hydrogen storage in the dehydrated prussian blue analogues M3[Co(CN)6]2 (M = Mn, Fe, Co, Ni, Cu, Zn)

The porosity and hydrogen storage properties for the dehydrated Prussian blue analogues M3[Co(CN)6]2 (M = Mn, Fe, Co, Ni, Cu, Zn) are reported. Argon sorption isotherms measured at 87 K afford BET surface areas ranging from 560 m2/g for Ni3[Co(CN)6]2 to 870 m2/g for Mn3[Co(CN)6]2; the latter value is comparable to the highest surface area reported for any known zeolite. All six compounds show significant hydrogen sorption at 77 K and 890 Torr, varying from 1.4 wt % and 0.018 kg H2/L for Zn3[Co(CN)6]2 to 1.8 wt % and 0.025 kg H2/L for Cu3[Co(CN)6]2. Fits to the sorption data employing the Langmuir-Freundlich equation give maximum uptake quantities, resulting in a predicted storage capacity of 2.1 wt % and 0.029 kg H2/L for Cu3[Co(CN)6]2 at saturation. Enthalpies of adsorption for the frameworks were calculated from hydrogen isotherms measured at 77 and 87 K and found to increase with M varying in the order Mn < Zn < Fe < Co < Cu < Ni. In all cases, the binding enthalpies, which lie in the range of 5.3-7.4 kJ/mol, are higher than the 4.7-5.2 kJ/mol measured for Zn4O(1,4-benzenedicarboxylate)3.     

[MPy4(NCO)2]-2Py clathrates (M = M(II) = Mn,Fe, Co,Ni, Cu,Zn, Cd; Py = pyridine)

The title compounds form an iso structural series and are isomorphic with other [MPy₄X₂]-2Py clathrates (XRD, KM4 diffractometer, cell parameters and space group Ccca from 17–80 reflections). In the clathrate [NiPy₄(NCO)₂]-2Py studied in detail (XRD, CAD-4 diffractom eter, λCuK_α, Ω/2θ scan mode, θ_max = 78‡, 990 strong reflections, 104 parameters, R = 0.053), the host molecule has 222 symmetry, and the twofold axes run along the coordination bonds. The transoctahedral environment of nickel consists of six nitrogen atoms of four pyridine and two isocyanate ligands. The coordination polyhedron is slightly distorted due to changes in the bond lengths. The molecule has a propeller conformation. The guest molecules lie in the cavities of the crystal structure in conformity with the van der Waals type of packing. The host complex [NiPy₄(NCO)₂] (XRD, CAD-4 diffractometer, 4615 strong reflections, 560 parameters, R-0.037) crystallizes in the triclinic crystal system (space group P1) with two independent asymmetric molecules in the unit cell. The molecular structure is analogous to that in the ciathrate phase, but the coordination angles are severely distorted; one of the molecules acquires a distorted propeller conformation, and the other, a centrosvmmetric conformation, which is less favorable. While being structurally identical, the [MPy₄(NCO)₂]-2Py clathrates differ heavily in the properties. The first four complexes dissociate to host complexes, and their thermal stability changes in the sequence Mn< Fe< Co< Ni; the Cu and Zn clathrates decompose in one step to dipyridine complexes with decomposition of host complexes. Decomposition of the Cd ciathrate follows one of these patterns depending on conditions. The results are compared with those for other known systems. Synthetic procedures are given. Translated fromZhurnal Strukturnoi Khimii, Vol. 40, No. 5, pp. 935–953, September–October, 1999.     

Cyano-bridged hexanuclear Fe4M2 (M = Ni, Co, Mn) clusters: spin-canted antiferromagnetic ordering of Fe4Ni2 cluster

Heterobimetallic hexanuclear cyano-bridged complexes, [{Fe(Tp)(CN)3}4{M(MeCN)(H2O)2}(2)].10H2O.2MeCN [M = Ni (1), Co (2), Mn (3); Tp = hydrotris(1-pyrazolyl)borate], have been synthesized in H2O-MeCN solution. Complexes 1-3 are isostructural and hexanuclear with [{Fe(Tp)(CN)3}4{M(MeCN)(H2O)2}2] units linked by hydrogen bonds to form a 2D-structure in the solid state. Complex 1 is a canted antiferromagnet that undergoes a field-induced spin-flop-like transition at approximately 1 T and 2 K. At 4.45 K 1 has a transition to paramagnetic state of noninteracting S = 4 magnetic clusters. However, 2 and 3 show antiferromagnetic intracluster coupling. Facile loss of solvent from 2 alters the local symmetry resulting in changing the intracluster interaction from antiferro- to ferromagnetic.     

Phase Transitions in Crystalline [M(H2O)6](ClO4)2 (M=Mg,Mn, Fe,Co, Ni,Cu, Zn,Cd and Hg)

The results of DSC measurements in the temperature range 140–370 K on nine crystalline compounds of the type [M(H₂O)₆](ClO₄)₂, where M=Mg, Mn, Fe, Co, Ni, Cu, Zn, Cd and Hg, are discussed. Anomalies detected in the DSC curves are related to the existence of solid-solid phase transitions and/or to the melting points of these compounds. In consequence of two different hypothetical structural modifications of [Fe(H₂O)₆](ClO₄)₂, two DSC curves are obtained. For the compounds with M=Fe, Cd and Hg, new phase transitions have been discovered. The transition temperatures of the other phase transitions are in good agreement with literature data obtained by adiabatic calorimetry. For the compounds with M=Mg, Ni and Cd, DTA measurements were also carried out and the melting points of theses compounds were established. This revised version was published online in August 2006 with corrections to the Cover Date.     

Schwingungsspektren der Bis(mercuriojodonium)-hexafluorometallate (HgJ)2MF6 (M = Ti,Zr, Sn) und verwandter Verbindungen

Vibrational Spectra of Bis (mercurioiodonium)-hexafluorometallates (HgI)₂ MF₆(M = Ti, Zr, Sn) and Similar Compounds For the isotypic bis(mercurioiodonium)-hexafluorometallates (HgI)₂MF₆ (M = Ti, Zr and Sn; space group D–Cmcm) with chain structure of the cations [(IHg_2/2)₂]²⁺ the complete vibrational spectra have been discussed on the basis of a factor group analysis. A simple model yields an average force constant f ? 1.37 N · cm^?1 for the Hg? I bonds of the chains and bond angles at the iodine atoms which agree satisfactorily with the data obtained by X-ray structure analysis. Spectra of (HgI)X (X = NO₃ and BF₄; benzene sulphonate and p-toluene sulphonate) also indicate cationic chains in these compounds.     

Thermochemistry of AII(VUO6)2 · nH2O Compounds (AII = Mn, Fe, Co, Ni, Cu, Zn, Cd)

Standard enthalpies of formation of uranovanadates of 3(4)d transition metals at 298.15 K were determined. The isobaric heat capacity of Co(VUO₆)₂ · 4H₂O was measured. The standard Gibbs functions of formation of the compounds were calculated on the basis of these data using approximate methods of absolute entropy calculation. The thermochemical characteristics of the synthesis and dehydration of uranovanadates were considered.     

Monodisperse MFe2O4 (M = Fe, Co, Mn) nanoparticles

High-temperature solution phase reaction of iron(III) acetylacetonate, Fe(acac)(3), with 1,2-hexadecanediol in the presence of oleic acid and oleylamine leads to monodisperse magnetite (Fe(3)O(4)) nanoparticles. Similarly, reaction of Fe(acac)(3) and Co(acac)(2) or Mn(acac)(2) with the same diol results in monodisperse CoFe(2)O(4) or MnFe(2)O(4) nanoparticles. Particle diameter can be tuned from 3 to 20 nm by varying reaction conditions or by seed-mediated growth. The as-synthesized iron oxide nanoparticles have a cubic spinel structure as characterized by HRTEM, SAED, and XRD. Further, Fe(3)O(4) can be oxidized to Fe(2)O(3), as evidenced by XRD, NEXAFS spectroscopy, and SQUID magnetometry. The hydrophobic nanoparticles can be transformed into hydrophilic ones by adding bipolar surfactants, and aqueous nanoparticle dispersion is readily made. These iron oxide nanoparticles and their dispersions in various media have great potential in magnetic nanodevice and biomagnetic applications.     

MII-N-diisopropoxythiophosphorylthiobenzamide complexing processes in M2[Fe(CN)6]-gelatin-immobilized matrices (M = Co,Ni, Cu)

Complexing processes in M^II-N-diisopropoxythiophosphorylthiobenzamide binary systems (M = Co, Ni, Cu) in metal(II) hexacyanoferrate(II) gelatin-immobilized matrices upon contact with aqueous–alkaline (pH = 12.0 ± 0.1) solutions of organic compounds have been studied. It has been shown that, in Co^II and Cu^II, the initial act of complexing involves destruction of the Co^II and Cu^II hexacyanoferrates(II) by OH^– ions, leading to formation of the corresponding hydroxides which react with the ligand indicated. In the both systems, successive addition of two ligand molecules per M(OH)₂ fragment occurs and [MB(OH)(OH₂)] and [MB₂] coordination compounds are formed (B^–-a singly deprotonated ligand form). In the Ni^II-N-diisopropoxythiophosphorylthiobenzamide system, the formation of three complexes, (Ni₂BOH)₂[Fe(CN)₆], [NiB(OH)(OH₂)] and [NiB₂] occurs.     

Complexation in Binary Cd2[Fe(CN)6]–M(II) Systems (M = Mn,Co, Ni,Cu, Zn) in Gelatin-Immobilized Cadmium(II) Hexacyanoferrates(II)

Complexation processes that occur between cadmium(II) hexacyanoferrate(II) (Cd₂[Fe(CN)₆]) and 3d-metal ions M(II) (M = Mn, Co, Ni, Cu, Zn) in thin gelatin layers with the immobilized cadmium(II) hexacyanoferrates when brought in contact with aqueous solutions of d-metal chlorides are studied. Cd²⁺ ions were found to be replaced to some extent by M²⁺ ions of the indicated d metals (except for Mn(II)) and form binuclear (dd)-metal hexacyanoferrates(II). A complete replacement of Cd(II) and formation of M₂[Fe(CN)₆] was observed in none of the cases.     

Magnetische Messungen anHeusler-Phasen (Co,Ni)2 XY (X=Ti,Zr, Hf,V und Mn;Y=Ge und Sn)

Magnetic measurements onHeusler alloys (Co, Ni)₂ XY are performed. The transitions from ferromagnetic to paramagnetic behaviour in some systems are of special interest.

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Mit 4 Abbildungen     

Linear-chain antiferromagnetism in the compounds MII(N2H5)2(SO4)2 with M = Mn,Fe, Co,Ni, and Cu

Powder-susceptibility measurements in the temperature region 2–80° K on the chain compounds M^II(N₂H₅)₂(SO₄)₂, with M = Mn, Fe, Co, Ni, and Cu, show that the magnetic properties of these compounds can be interpreted in terms of antiferromagnetic linear-chain systems. The experimental results provide information on the magnitude of the intrachain interactions. In addition, ESR linewidth experiments were used for a determination of the intrachain interaction in Mn(N₂H₅)₂ (SO₄)₂. For the interpretation of the data on Fe(N₂H₅)₂(SO₄)₂, the parallel susceptibility of Ising chains with S = 2 is calculated theoretically. An estimate for the ratio between the intra- and interchain coupling is given. Use is made of preliminary results of specific heat measurements on these compounds for the interpretation of the magnetic data.     

Order and disorder in mixed metal linear chains: The homo and heterobimetallic EDTA (M(H2O)4OIOII)[M′(EDTA)] · 6H2O complexes (M = Mg,Mn, Co,Zn and Ni; M′ = Co,Ni, Cu and Zn)

Summary Polymetallic solid solutions of the ethylenediaminetetracetic acid (EDTA) and six divalent metal ions exist in the range: MgMnCoZnNiCu(EDTA) · 6H₂O where + + + + + =2, 01, 0,,2, 0, 1.This type of structure is characterized by the presence of two different octahedral carboxylate-bridged coordination sites forming infinite zig-zag chains. Visible and i.r. spectra and t.g.a. analysis show that there is occupational preference for the two coordination sites in the crystalline structure.Due to this preference, and also to the structural features, the heterobimetallic MM(EDTA) · 6H₂O compounds constitute a structurally new class of materials which can be described as ordered alternating-heterobimetallic polymeric coordination complexes.     

Synthese und Eigenschaften der Di‐tert‐butylphosphide [M(PtBu2)2]2 (M = Zn,Hg) und [Cu(PtBu2)]4

Syntheses and Properties of Di‐tert‐butylphosphides [M(PtBu₂)₂]₂ (M = Zn, Hg) and [Cu(PtBu₂)]₄ The phosphides [M(PtBu₂)₂]₂ (M = Zn, Hg) and [Cu(PtBu₂)]₄ are accessible from reaction of LiPtBu₂ with ZnI₂, HgCl₂ and CuCl, respectively. [M(PtBu₂)₂]₂ (M = Zn, Hg) are dimers in the solid state. X‐ray structural analyses of these phosphides reveal that [M(PtBu₂)₂]₂ (M = Zn, Hg) contain four‐membered M₂P₂‐rings whereas [Cu(PtBu₂)]₄ features a planar eight‐membered Cu₄P₄‐ring. Degradation reaction of LiPtBu₂(BH₃) in the presence of HgCl₂ results in the dimeric phosphanylborane BH₃ adduct [tBu₂PBH₂(BH₃)]₂. X‐ray quality crystals of [tBu₂PBH₂(BH₃)]₂ (monoclinic, P2₁/n) are obtained from a pentane solution at 6 °C. According to the result of the X‐ray structural analysis, the O₂‐oxidation product of [Hg(PtBu₂)₂]₂, [Hg{OP(O)(tBu)OPtBu₂}(μ‐OPtBu)]₂, features in the solid state structure two five‐membered HgP₂O₂‐rings and a six‐membered Hg₂P₂O₂‐ring. Herein the spiro‐connected Hg atoms are member of one five‐membered and of the six‐membered ring.     

Zur Polymorphie und Pseudosymmetrie der Hydrate MSeO3 · H2O (M = Mn,Co, Ni,Zn, Cd)

Polymorphic and Pseudosymmetrical Hydrates MSeO₃ · H₂O (M = Mn, Co, Ni, Zn, Cd) By crystallization from aqueous solutions of MSeO₃ and M(HSeO₃)₂, the selenites MSeO₃ · H₂O (M = Mn, Co, Ni, Zn, Cd) were obtained and characterized by means of X-ray diffraction and IR-spectroscopy. The crystal structure of ZnSeO₃ · H₂O was determined. The IR spectra indicate that the hydrates are isotypic and contain H₂O molecules of symmetry mm2. However, the X-ray data show different structure types with H₂O molecules of site symmetry m or 1. CdSeO₃ · H₂O and MnSeO₃ · H₂O are isotypic (o.rh., MnSeO₃ · D₂O type). CoSeO₃ · H₂O (mon.) as well as the isotypic NiSeO₃ · H₂O and ZnSeO₃ · H₂O (mon.) form new structure types. These findings are discussed on the basis of the crystal structure of ZnSeO₃ · H₂O (P2₁/n, a = 477.9(1), b = 1319.4(5), c = 570.1(1) pm, β = 90.84(2)°, Z = 4, D_x = 3.886 g · cm^?3, R = 0.035 for 722 reflections with I > 2σ₁) and the local pseudosymmetry of its components, i.e., layers [ZnSeO₃ · H₂O] of ZnO₆ octahedra sharing four equatorial vertices, SeO₃^2? anions and H₂O molecules.