Darstellung und spektroskopische Charakterisierung von Kupfer(II)- und Nickel(II)-tricyanmethanid-Komplexen mit Imidazol-Derivaten – Kristallstruktur von [Cu{C(CN)3}2(2-meiz)2]

Synthesis and Spectroscopic Characterization of Copper(II) and Nickel(II) Tricyanomethanide Complexes with Imidazoles – Crystal Structure of [Cu{C(CN)₃}₂(2-meiz)₂] The copper(II) and nickel(II) tricyanomethanide complexes with imidazoles of the type [Cu{C(CN)₃}₂L₄], [L = 2- or 4-methylimidazole (meiz)] and [M{C(CN)₃}₂L₂] [M = Cu, L = imidazole (iz), 2- or 4-meiz; M = Ni, L = iz, 2- or 4-meiz] were prepared and characterized by electronic, infrared, and – some of them – by ESR spectroscopy. The structure [Cu{C(CN)₃}₂(2-meiz)₂], solved by X-ray crystallographic analysis, shows a two-dimensional network with unsymmetric C(CN)₃-bridges between the Cu^II atoms. Polymeric structures with bridging C(CN)₃-groups were identified by means of spectroscopic methods also for the other [M{C(CN)₃}₂L₂] complexes. On the other hand, for the complexes [M{C(CN)₃}₂L₄] follow molecular structures, in which monodentate C(CN)₃ ligands are present. All compounds under investigation show a tetragonal-bipyramidal geometry with various degree of tetragonal distortion.     

Metall-Pseudohalogenide. XL. Zur Kenntnis anionischer Dicyanamidkomplexe [M{N(CN)2}4]2− des Palladium(II) und Platin(II)

Metal Pseudohalides. XL. Dicyanamido Metallates [M{N(CN)₂}₄]^2? of Palladium(II) and Platinum(II) The synthesis of homologeous tetrakis-(dicyanamido) metallates(II), [M{N(CN)₂}₄]^2? is reported. The coordination type of the ambivalent dicyanamide ligand is discussed on the basis of the i.r. and n.m.r. spectra of the new complexes.     

Thermal N(CN)2-bridging reactions of dicyanamide complexes Ni{N(CN)2}2Ln in solid phase

The stoichiometry of thermal decomposition reactions was studied for the following compounds: Ni{N(CN)₂}_2py2 (I) (py-pyridine), Ni{N(CN)₂}₂(2-Mepy)₂ (II), Ni{N(CN)₂}₂(3-Mepy)₂ (III) and Ni{N(CN)₂}₂(4-Mepy)₃ (IV). In complexes I and II the loss of the volatile heterocyclic ligands occurs in one step while in complexes III and IV in two steps. Magnetic and spectral data indicated pseudooctahedral configuration for all complexes. The course of thermal N(CN)₂-bridging reactions of the complexes studied are discussed. Part XXV in the series Heterogeneous reactions of solid Ni(II) complexes.     

Metall-Pseudohalogenide. XLIII. Anionische Tricyanmethanid-Komplexe des Palladium (II) und Platin (II)

Metal Pseudohalides. XLIII. Anionic Tricyanomethanide Complexes of Palladium (II) and Platinum (II) The synthesis of homogeneous tricyanmethanido metallates(II) of the type [(C₆H₅)₄E]₂[M{C(CN)₃}₄] (M: Pd, Pt; E: P, As) is reported. I.R., ¹³C-N.M.R., and ESCA investigation are indicating for these complexes relative weak metal-ligand interactions.     

Magnetic and spectral properties of the coligand isomer pair: Cu{N(CN)2}2(pyrazole)2 and Cu{pyrazole · N(CN)2}2

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.     

Anionische Nickel-Pseudohalogenid-Komplexe der Typen [Ni{N(CN)2}3]− und [Ni{N(CN)2}2(NCS)2]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.     

Nickel(II) complexes with dicyanamide and tetramines

Four new pseudohalide complexes of the type [NiL{N(CN)₂}₂] (L = N(CH₂CH₂NH₂)₃, TAA; triethylenetetramine, TTA) and [NiL{N(CN)₂}]ClO₄ have been prepared and characterized by spectroscopic and magnetic methods. The X-ray crystal structures of [Ni(TAA){N(CN)₂}₂] and [Ni(TTA){N(CN)₂}₂] have been determined, and analyses show that in both complexes the Ni ion posseses distorted octahedral geometry. The temperature dependence of the magnetic susceptibility of [Ni(TTA){N(CN)₂}](ClO₄) was measured, but no antiferromagnetic interaction was detected.     

Synthesis,structure and magnetic properties of 2-D and 3-D [cation]{M[Au(CN)2]3} (M = Ni, Co) coordination polymers

In order to study the templating effect of the cation and the resulting impact on the magnetic properties, reactions of M(II) salts with [cation][Au(CN)₂] were conducted, yielding a series of coordination polymers of the form [cation]{M[Au(CN)₂]₃} (cation = ⁿBu₄N⁺, PPN⁺ (bis(triphenylphosphoranylidene)ammonium); M = Ni(II) and Co(II)). The structures of ⁿBu₄N{M[Au(CN)₂]₃} and PPN{M[Au(CN)₂]₃} (M = Ni and Co) contain two distinct 3-D anionic frameworks of {M[Au(CN)₂]₃}⁻, hence the framework was sensitive to the cation, but not to the identity of the metal center. In ⁿBu₄N{M[Au(CN)₂]₃}, the metal centers are connected by [Au(CN)₂] units to form six 2-D (4, 4) rectangular grids that are fused through the M centers to yield a complex three-dimensional framework which accommodates the ⁿBu₄N⁺ cations. In PPN{M[Au(CN)₂]₃}, the framework adopts a simpler non-interpenetrated Prussian-blue-type pseudo-cubic array, with the PPN⁺ cations occupying each cavity; no reduction in dimensionality occurs despite the large cation size. In the presence of water, {Co(H₂O)₂[Au(CN)₂]₂} · ⁿBu₄N[Au(CN)₂] was obtained, a 2-D layered polymer that contains neutral sheets of {Co(H₂O)₂[Au(CN)₂]₂} which are separated by ⁿBu₄N[Au(CN)₂] layers; aurophilic interactions of 3.4250(13) Å and hydrogen-bonding connect the layers. The magnetic properties of all compounds were investigated by SQUID magnetometry. The Ni(II) polymers have similar magnetic behaviour, which are dominated by zero-field splitting with very weak antiferromagnetic interactions at low temperature (D ∼ 2–3 cm⁻¹, zJ < 1 cm⁻¹). The magnetic behaviour of all of the Co(II) polymers were found to be very similar, and dominated by single-ion effects (i.e. a large first-order orbital contribution). No significant magnetic coupling is observed in any of these coordination polymers, suggesting that the [Au(CN)₂] bridging unit behaves as a poor mediator of magnetic exchange in these high-dimensionality systems.     

An infrared and raman spectroscopic study of metal(II) Di(2-methylpyridine) tetracyanonickelate complexes: Ni(C6H7N)2Ni(CN)4 and Cd(C6H7N)2Ni(CN)4

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.     

Structural Organization of Nickel(II), Zinc(II), and Copper(II) Complexes with Diisobutyldithiocarbamate: EPR, <Superscript>13</Superscript>C and <Superscript>15</Superscript>N CP/MAS NMR,and X-Ray Diffraction Studies

The structures and spectroscopic properties of nickel(II), zinc(II), and copper(II) complexes with dibutyl- and diisobutyldithiocarbamate were studied by EPR and ¹³C and ¹⁵N CP/MAS NMR spectroscopy and X-ray diffraction analysis. According to the EPR data, copper(II) forms mononuclear [^63/65Cu{S₂CNR₂}₂] and heterobinuclear complexes [^63/65CuZn{S₂CNR₂}₄] under magnetic dilution conditions. The isomeric forms of nickel(II) and zinc(II) diisobutyldithiocarbamates were detected by ¹³C and ¹⁵N NMR spectroscopy. The crystalline zinc(II) diisobutyldithiocarbamate was found to have a unique structural organization with alternating mononuclear [Zn{S₂CN(i-C₄H₉)₂}₂] and binuclear molecular forms [Zn₂{ S₂CN(i-C₄H₉)₂}₄] in the 1 : 1 ratio.     

Clathrate and inclusion compounds: Part V. An infrared and Raman study of the decomposition of the Hofmann aniline clathrates M(NH3)2Ni(CN)4.2C6H5NH2 {M = Cd(II) and Ni(II)}

The time-dependent changes which are observed in the infrared and Raman spectra of samples of the two Hofmann aniline clathrates M(NH₃)₂Ni(CN)₄.an₂ {M = Cd(II), Ni(II), an = C₆H₅NH₂} indicate the occurrence of a solid state ligand replacement reaction in which the aniline guest molecule replaces the coordinated ammonia to give Man₂Ni(CN)₄ as the final product. The rate of replacement is greater for the cadmium than for the nickel clathrate, and for both clathrates evacuation of the sample greatly increases the rate of replacement. The Man₂Ni(CN)₄ complexes can themselves act as host lattices forming clathrates containing guest molecules such as aniline.     

Metal complexes of sulfur-nitrogen chelating agents. Part 12. The chemistry of nickel(II), palladium(II), cobalt(II) and copper(II) complexes of N2S2 and N3S2 donor systems

Summary Nickel(II), palladium(II), cobalt(II) and copper(II) complexes of the ligandN,N-1,2-propane-bis(methyl 2-amino-cyclopent-1-ene-dithiocarboxylate) (H₂L¹),N,N-1,3-propane-bis(methyl 2-aminocyclopent-1-ene-dithiocarboxylate) (H₂L²) andN,N-[bis(methyl 2-aminocyclopent-1-ene-dithiocarboxylate)] diethylenetriamine (H₂L³) have been synthesised. Both H₂L¹ and H₂L² form complexes of the type ML, and all but the copper(II) complexes, are square planar. In the copper(II) complexes tetrahedral distortion is significantly more with CuL². From H₂L³ square planar complexes of the type [M(HL³)X] (M=Ni, X=Cl, Br, I or SCN; M=Pd, X=Cl or Br) have been obtained in which the donor unit involved is N₂SX. The composition of the cobalt(II) and copper(II) complexes is [M(H₂L³)X₂] (X=Cl or Br) which contain the chromophore [MN₃X₂].     

两个含有平行交替链的新型二氰胺配位高聚物: {Mn(dmpz)[N(CN)2]2}2和{Cu(dmpz)[N(CN)2]2}2

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.     

Strukturelle Charakterisierung der Dicyanamid-Komplexe von Kupfer(II), Nickel(II) bzw. Kobalt(II) mit Aminopyridinen

Summary New dicyanamide complexes of the typeM[N(CN)₂]₂ L ₂ (M=Cu or Ni;L=2-, 3-, 4-aminopyridine, 2-amino-5-nitropyridine) and Co[N(CN)₂]₂ (2-amino-5-nitropyridine)₂ were prepared and studied by spectroscopic methods as well as by room-temperature magnetic moments. The results show that the Cu(II) complexes have elongated pseudooctahedral structures while the Ni(II) and Co(II) complexes are octahedral. In most cases the N(CN)₂ groups are in bridging function and through their cyanide nitrogens, or-more rarely-amide and cyanide nitrogens connect the basic structure units into polymeric conglomerates. In the Cu(II) systems exchange coupling is seen from the _eff value or ESR spectrum.

Professor Viktor Gutmann zum 70. Geburtstag gewidmet     

Raman-spektroskopische Untersuchungen an koordinationspolymeren Metall-tricyanmethaniden M[C(CN)3]2

Raman Spectroscopic Investigations of Coordination Polymeric Metal Tricyanmethanides The Raman spectra of 3d-metal tricyanmethanides M{C(CN)₃}₂ as well as of [Ni{C(CN)₃}₂py₂] are investigated. The observed Raman lines are assigned, characteristic variations of position and intensity of these lines are discussed.     

Thermal and spectral studies of 5-(phenylazo)-2-thiohydantoin and 5-(2- hydroxyphenylazo)-2-thiohydantoin complexes of cobalt(II), nickel(II) and copper(II)

Complexes of 5-(phenylazo)-2-thiohydantoin (L¹) and 5-(2-hydroxyphenylazo)-2-thiohydantoin (HL²) with Co(II), Ni(II) and Cu(II) salts have been synthesised and characterized by elemental analysis, conductivity, magnetic susceptibility, UV-Vis, IR, ESR and TG studies. The magnetic and spectral data suggested octahedral geometry for [L¹M(OAc)₂(H₂O)₂]·xH₂O {M=Ni^ll and Cu^ll} and [L¹CuCl₂(H₂O)]·H₂O (dimeric form for the latter), trigonal bipyramidal geometry for [L²Co(OAc)(H₂O)]·2H₂O, square pyramidal geometry for [L²Ni(OAc)(H₂O)]·H₂O and square planar geometry for [L²CuCl]·2H₂O. TG studies confirmed the chemical formulations of these complexes and showed that their thermal degradation takes place in three to five steps, depending on the type of the ligand and the geometry of the complex. The kinetic parameters (n, E^#, A, ΔH^#, ΔS^# and ΔG^#) of the thermal decomposition stages were computed using the Coats-Redfern and other standard equations and are discussed.     

Raman-spektroskopische Untersuchungen an Metall-dicyanamiden

Raman Spectroscopic Investigations of Metal Dicyanamides The Raman spectra of 3d metal dicyanamides M{N(CN)₂}₂ (M ? Mn, Fe, Co, Ni, Cu, Zn) and some pyridine complexes [M{N(CN)₂}₂py₂] are investigated. Characteristic variations of these frequencies depending on different parameters are discussed.     

Struktur und thermische Zersetzung von Bis(triethanolamin)kupfer(II)-acetat [Cu{N(CH2CH2OH)3}2](CH3COO)2

Structure and Thermal Decomposition of Bis(triethanolamine)copper(II) Acetate [Cu{N(CH₂CH₂OH)₃}₂](CH₃COO)₂ Bis(triethanolamine)copper(II) acetate [Cu{N · (CH₂CH₂OH)₃}₂](CH₃COO)₂ was prepared using the basic components; the structure was determined by single crystal X-ray diffraction. The complex crystallizes in the monoclinic space group P2₁/c with a = 9.101 Å, b = 13.136 Å, c = 9.819 Å, β = 111.63°. Details of the synthesis, X-ray data, and the thermal decomposition are reported.     

Synthesis,structure, and thermal properties of benzene-solvated forms of bis(dimethyldithiocarbamato)piperidinezinc and -copper(II)

Solvated adducts of zinc and copper(II) dimethyldithiocarbamate complexes with piperidine of the general formula [M{NH(CH₂)₅}{S₂CN(CH₃)₂}₂] · C₆H₆ (M = Zn (I), ⁶³Cu (II)) were isolated on a preparative scale. According to X-ray diffraction data, compound I has a clathrate type structure: the benzene molecules located between the coordinated piperidine rings of neighboring adduct molecules are held by hydrogen bonds. Thermal destruction of I studied by simultaneous thermal analysis includes the desorption steps of benzene solvate molecules and inner-sphere piperidine molecules and thermolysis of the “dithiocarbamate part” of the adduct to give ZnS as the final product. The triaxial anisotropy pattern of EPR parameters of the isotope-substituted magnetically diluted adduct II indicates that the geometry of the copper coordination polyhedron is intermediate between a tetragonal pyramid (TP) and trigonal bipyramid (TBP). It was shown solvation of the adduct [⁶³Cu{NH(CH₂)₅}{S₂CN(CH₃)₂}₂] resulting a considerable increase in the contribution of the TBP component.     

Vibrational spectroscopic studies of 4,4′-bipyridyl metal(II) tetracyanonickelate complexes and their clathrates

The infrared spectra of M(4,4-bipyridyl)Ni(CN)₄ complexes (M=Ni or Cd) and their dioxane, benzene, toluene, aniline andN,N-dimethylaniline clathrates are reported. Additional information regarding the structure of the host lattice is obtained from the Raman spectra of the M=Cd complex. It is shown that the structure of the host lattice consists of infinite polymeric layers of {M-Ni(CN)₄} analogous to those of Hofmann type clathrates that have tetragonal symmetry. Bidentate 4,4-bipyridyl molecules form bridges between the metal atoms {M} in the adjacent {M-Ni(CN)₄} layers. It is found that the 4,4-bipyridyl molecules are centrosymmetric in this structure.Presented at the Fourth International Symposium on Inclusion Phenomena and the Third International Symposium on Cyclodextrins, Lancaster, U.K., 20–25 July 1986