Vibrational spectroscopic studies on the en-Td-type benzene clathrates: M(ethylenediamine)M′(CN)4·2C6H6 (M=Mn or Cd,M′=Cd or Hg)

IR spectra of Mn(en)M(CN)₄·2C₆H₆ (M=Cd or Hg), and IR and Raman spectra of Cd(en)M(CN)₄·2C₆H₆ (M=Cd or Hg) clathrates are reported. The spectral features suggest that the first two compounds are similar in structure to the later two Td-type clathrates.     

Vibrational spectroscopic studies on the hofmann-Td-type clathrates: M(NH3)2M′(CN)4·2C6H6 (M=Mn or Cd and M′=Cd or Hg0

IR spectra of Mn(NH₃)₂M(CN)₄·2C₆H₆ (M=Cd or Hg), and IR and Raman spectra of Cd(NH₃)₂M(CN)₄·2C₆H₆ (M=Cd or Hg) are reported. The spectral data suggest that the former two compounds are similar in structure to the latter two Td-type clathrates.     

Vibrational Spectroscopic Studies on the Td-type Adeninemetal(II)tetracyanometallate(II) Benzene Clathrates: M(ad)2M'(CN)4.C6H6 (M = Mn or Cd, M' = Cd or Hg)

IR spectra of Mn(adenine)₂M(CN)₄.C₆H₆ (M=Cd or Hg), andIR and Raman spectra of Cd(adenine)₂M(CN)₄.C₆H₆(M=Cd or Hg) are reported. The spectral data suggest thatthe host frameworks of these compounds are similarto those of the Hofmann-T_d-type and the adeninecoordination is via N(10).     

Infrared Spectroscopic Study on the Hofmann Td-Type Clathrates: Mn(NH3)2M(CN)4·2 C6H5NH2 (M = Zn, Cd or Hg)

Infrared spectra of Mn(NH₃)₂M(CN)₄·2C₆H₅NH₂ (M = Zn, Cd or Hg) are reported. The spectral data suggest that these compounds are similar in structure to Hofmann-T_d-type clathrates.     

An Infrared Spectroscopic Study on the Hofmann T d -Type Clathrates: M(Imidazole) 2 M'(CN) 4 .2C 6 H 6

Infrared spectra of M (Imidazole)2 M' (CN)₄ 2C₆H₆ (M = Mn, Co,Ni, Cd; M' = Zn, Cd) are reported. The spectral data suggest that the clathratesare similar in host structure to of Hofmann T_d-type clathrates.     

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.     

An Infrared Spectroscopic Study on the Hofmann- and en-Td-type Clathrates: Mn(NH3)2Zn(CN)4 .2benzene and Mn(ethylenediamine)Zn(CN)4.2benzene

Infrared spectra of Mn(NH₃)₂Zn(CN)₄.2C₆H₆ andMn(ethylenediamine)Zn(CN)₄.2C₆H₆ are reported. The spectral data suggest that these compounds are similar in structure toHofmann-T_d-type and the en-T_d-type clathrates,respectively. There is good evidence for H-bonding from ammoniaN–H to benzene as a to H-bond.     

Vibrational Spectroscopic Studies on the Hofmann-dabn-Type Benzene Clathrates: M(1,4-diaminobutane)Ni(CN)4° 1.5C6H6 (M = Mn, Fe, Co, Ni or Cd)

IR spectra of M(1,4-diaminobutane)Ni(CN)4° 1.5C6H6 (M = Mn, Fe, or Co), and IR and Raman spectra of M(1,4-diaminobutane)Ni(CN)4° 1.5C6H6 (M = Ni or Cd) clathrates are reported. The spectral features suggest that the compounds are similar in structure to the Hofmann-dabn-type clathrates.     

Über die Darstellung von Tricyanmethanidometallbromiden und Organometalltricyanmethaniden durch Reaktionen mit Bromtricyanmethan BrC(CN)3

Different reactions of BrC(CN)₃ with metal bromides (MBr₄; M = Sn, Ti, Zr), metal organyles (SnR₄, MR₂ (R = C₂H₅, C₆H₅; M = Zn, Cd), C₆H₅HgBr) and with phosphorus tribromide are reported. These reactions lead to the formation of new compounds of the types MBr₃NCC(CN)₂, R₃MNCC(CN)₂, RMNCC(CN)₂ and PBr₄NCC(CN)₂, respectively. The structures of the new compounds are discussed, using results of infrared spectroscopic measurements. Mostly the pseudohalide group C(CN)₃ is bonded to the metal via the nitrogen of a cyano group. Unsolubility and IR spectra are characterizing the compounds of the types MBr₃NCC(CN)₂ and RMNCC(CN)₂ as coordination polymers. IIb-metal derivatives form pyridine complexes [RMNCC(CN)₂(C₅H₅N)₂].     

Die Kristallstruktur des „supramolekularen”︁ Cadmiumcyanid-Hexamethylentetramin-Addukts [Cd(CN)2 · 2/3 C6H12N4]

The Crystal Structure of the “Supramolecular” Cadmiumcyanide-Hexamethylenetetramine Adduct [Cd(CN)₂ · 2/3 C₆H₁₂N₄] Single crystals of a new compound in the system Cd(CN)₂-hexamethylenetetramine (HMTA) with the composition [Cd(CN)₂ · 2/3 C₆H₁₂N₄] were obtained by crystallization from an aqueous solution containing Cd(CN)₂ and HMTA. The structure consists of a ?supramolecular”? network of ? Cd? CN? Cd- and ? Cd? HMTA? Cd-chains. The structure is compared with that of an already known compound [Cd(CN)₂ · 1/3 C₆H₁₂N₄].     

Untersuchungen zu Synthese und Reaktionen von Fluorphenylquecksilber-Derivaten mit den Liganden 2-FC6H4, 2,6-F2C6H3 und 2,4,6-F3C6H2

Investigations on Syntheses and Reactions of Fluorophenylmercury Compounds with the Ligands 2-FC₆H₄, 2,6-F₂C₆H₃, and 2,4,6-F₃C₆H₂ 2,6-F₂C₆H₃HgCl and 2,4,6-F₃C₆H₂HgCl are synthesized via the reactions of the corresponding phenylmagnesium compounds and HgCl₂. 2-FC₆H₄HgCl is selectively obtained only in a reaction involving intermediately formed Cd(2-FC₆H₄)₂. The diphenylmercury derivative Hg(2,4,6-F₃C₆H₂)₂ is obtained while stirring a dichloromethane solution of 2,4,6-F₃C₆H₂HgCl for several days. The direct mercuration of 1,3,5-trifluorobenzene with Hg(OCOCF₃)₂ yields, depending on the stoichiometry, 2,4,6-trifluorophenylmercury trifluoroacetate and 1,3-bis(trifluoroacetatomercuri)-2,4,6-trifluorobenzene which is converted into the corresponding chloromercuri derivative by treatment with hydrochloric acid in CH₃CN. As a product of the reaction of 1,3,5-trifluorobenzene and HgO in CH₃COOH only 2,4,6-trifluorophenylmercury acetate is isolated although spectroscopic evidence has been found for double and triple mercurated derivatives. All compounds are characterized by elemental analyses, nmr and mass spectra. The reaction of Hg(2,4,6-F₃C₆H₂)Cl and Cd(CF₃)₂ · 2 CH₃CN gives Hg(2,4,6-F₃C₆H₂)CF₃ which slowly dismutates in CH₂Cl₂ solution into Hg(2,4,6-F₃C₆H₂)₂ and Hg(CF₃)₂. The ligand exchange of Hg(2,4,6-F₃C₆H₂)₂ and TeCl₄ selectively gives Te(2,4,6-F₃C₆H₂)₂Cl₂ and Hg(2,4,6-F₃C₆H₂)Cl. Transmetalations of Hg(2,4,6-F₃C₆H₂)₂ and gallium or tin give NMR spectroscopic evidence for the new derivates Ga(2,4,6-F₃C₆H₂)₃ and Sn(2,4,6-F₃C₆H₂)₄.     

Spektroskopische Untersuchungen an Eisen(II)-nitrosodicyan-methanid- und -nitrosocarbamoylcyanmethanid-Komplexen [Fe(NOC(CN)2)2(C5H5N)4] und [Fe(NOC(CN)C(O)NH2)2(C5H5N)2]

Spectroscopic Investigations of the Iron(II) Nitrosodicyanomethanide and Nitrosocarbamoylcyanomethanide Complexes [Fe(NOC(CN)₂)₂(C₅H₅N)₄] and [Fe(NOC(CN)C(O)NH₂)₂(C₅H₅N)₂] The syntheses of new iron(II) complexes of the nonlinear pseudohalides [NOC(CN)₂]^? and [NOC(CN)C(O)NH₂]^? is reported. The Structures of the compounds are discussed on the basis of IR, Mößbauer, ¹³C, and ¹⁴N NMR spectra as well as of the results of magnetic measurements.     

Cubane Tellurido Clusters [Zn(NH3)4]3[Mo4Te4(CN)12] and [Cd(NH3)4]3[W4Te4(CN)12]: Syntheses and Crystal Structures

Single crystals of [Zn(NH₃)₄]₃[Mo₄Te₄(CN)₁₂] (I) and [Cd(NH₃)₄]₃[W₄Te₄(CN)₁₂] (II) were obtained by applying solutions of K₇[Mo₄Te₄(CN)₁₂] · 11H₂O and K₆[W₄Te₄(CN)₁₂] · 5H₂O in aqueous ammonia over solutions of ZnCl₂ and Cd(NO₃)₂ in glycerol and were characterized by X-ray diffraction analysis. The IR spectra and thermal properties of compounds I and II were examined.     

Spectral,thermal and magnetic investigations of Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) 4-methylphthalates

Conditions for the preparation of Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) 4-methylphthalates were investigated and their composition, solubility in water at 295 K and magnetic moments were determined. IR spectra and powder diffraction patterns of the complexes prepared with molar ratio of metal to organic ligand of 1.0:1.0 and general formula: M [ CH₃C₆H₃(CO₂)₂]·nH₂o (n=1-3) were recorded and their decomposition in air were studied. During heating the hydrated complexes are dehydrated in one (Mn, Co, Ni, Zn, Cd) or two steps (Cu) and next the anhydrous complexes decompose to oxides directly (Cu, Zn), with intermediate formation of carbonates (Mn, Cd), oxocarbonates (Ni) or carbonate and free metal (Co). The carboxylate groups in the complexes studied are mono- and bidentate (Co, Ni), bidentate chelating and bridging (Zn) or bidentate chelating (Mn, Cu, Cd). The magnetic moments for paramagnetic complexes of Mn(II), Co(II), Ni(II) and Cu(II) attain values 5.92, 5.05, 3.36 and 1.96 M.B., respectively. This revised version was published online in July 2006 with corrections to the Cover Date.     

Charakterisierung von Distorsionsisomeren der Anionen Pentacyano-oxo-molybdat(IV) sowie Tetracyano-oxo-aqua-molybdat(IV) im festen Zustand. Kristallstrukturen von [(C6H5)4P]3[MoO(CN)5] · 7 H2O(grün), [(C6H5)4As]2 [MoO(OH2)(CN)4] · 4 H2O (blau) und [(C6H5)4P]2[MoO(OH2)(CN)4] · 4 H2O (grün)

Characterization of Distortional Isomers of the Anions Pentacyano-oxo-molybdate(IV) and of Tetracyano-aqua-oxo-molybdate(IV) in the Solid State. Crystal Structures of [(C₆H₅)₄P]₃[MoO(CN)₅] · 7 H₂O (green), [(C₆H₅)₄As]₂[MoO(OH₂)(CN)₄] · 4 H₂O (blue), and [(C₆H₅)₄P]₂[MoO(OH₂) (CN)₄] · 4 H₂O (green) Preparation of a series of salts containing the new pentacyano-oxo-molybdate(IV) anion is described: Cs₂H[MoO(CN)₅] (blue), [(CH₃)₄N]₂H[MoO(CN)₅] · 2 H₂O (blue) and [Cr(en)₃] [MoO(CN)₅] · 4 H₂O (green). The green [(C₆H₅)₄P]₃[MoO(CN)₅] · 7 H₂O crystallizes triclinic in the space group P1 . The molybdenum(IV) center is in an pseudo-octahedral environment of a terminal oxo-group (d(Mo?O); 1.705(4) Å), a CN^? group in the trans-position (d(Mo? C): 2.373(6) Å), and four equatorial CN^? groups (averaged d(Mo? C): 2.178 (Å). The blue and green salts exhibit v(Mo?O) stretching frequencies at 948 cm^?1 and 920 cm^?1, respectively. Blue and green salts containing the [MoO(OH₂)(CN)₄]^2? anion and [(C₆H₅)₄P]⁺ or [(C₆H₅)₄As]⁺ cations have been prepared and characterized by single crystal crystallography. [(C₆H₅)₄P]₂[MoO(OH₂)(CN)₄] · 4 H₂O (green) and [(C₆H₅)₄As]₂[MoO(OH₂)(CN)₄] · 4 H₂O (blue) crystallize monoclinic in the space group C—P2₁/n. They are considered to be distortional isomers of the complex anion: the green species has a Mo?O bond distance of 1.72(2) Å whereas for the blue species d(Mo?O) = 1.60(2) Å is found; the corresponding v(Mo?O) frequencies are at 920 cm^?1 and 980 cm^?1.     

M[B(CN)4]2: Zwei neue Tetracyanoborate mit zweiwertigen Kationen (M = Zn,Cu)

M[B(CN)₄]₂: Two new Tetracyanoborate Compounds with divalent Cations (M = Zn, Cu) The reaction of ZnO or CuO with [H₃O][B(CN)₄] in aqueous solution yielded single crystals of Zn[B(CN)₄]₂ and Cu[B(CN)₄]₂, respectively. The compounds were characterized by single‐crystal X‐ray diffraction. Zn[B(CN)₄]₂ ( (no. 164), a = b = 7.5092(9) Å, c = 6.0159(6) Å, Z = 1) crystallizes isotypic with Hg[B(CN)₄]₂. The structure of Cu[B(CN)₄]₂ (C2/m (no. 12), a = 13.185(3) Å, b = 7.2919(9) Å, c = 6.029(1) Å, β = 93.02(2)°, Z = 2) can be considered as a super‐structure, resulting from Jahn‐Teller distortion of the Cu²⁺ ions. Magnetic measurements were performed for the copper compound. Vibrational spectra and thermal stabilities were compared with the known mercury(II) tetracyanoborate.     

Spectroscopic,crystal structure and thermal studies of Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II) with 5-amino-4-arylazo-3-methyl-1-phenylpyrazole (aryl=C6H5,o-C6H4COOH,o-C6H4OH)

5-Amino-4-arylazo-3-methyl-1-phenylpyrazole (aryl?=?C₆H₅,o-C₆H₄COOH,o-C₆H₄OH) and its complexes with Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II) ions were synthesized. The complexes are in the ratio 1?:?1 and 1?:?2 (metal?:?ligand). Ligands and complexes were subjected to elemental analysis, IR, Raman, UV-Vis and ¹H-NMR spectroscopy. The mass spectra of the ligands were discussed. Thermal analysis and magnetic measurements were carried out for the prepared complexes. The X-ray single crystal structure of [Ni(L1)₂] was performed. The investigated pyrazole compounds coordinate as bidentate ligands through amino and azo nitrogens or tridentate through NNO. The molar conductance of the chelates is measured and reflected the non-electrolytic nature of the prepared complexes.     

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.     

Synthese von Clathratverbindungen des Typs Cd(mea) m [Pd(CN)4] ·nG

The preparation, identification and some properties of three new clathrate compounds Cd(mea)[Pd(CN)₄] · 2C₆H₆, Cd(mea)₂[Pd(CN)₄] · C₄H₄S and Cd(mea)₂[Pd(CN)₄] · C₄H₄NH (mea = HO-CH₂-CH₂-NH₂) are described.

     

An infrared and Raman spectroscopic study of the Hofmann-type complexes and clathrates: M(piperidine)2Ni(CN)4; M(piperidine)2Ni(CN)4·1.5G (M=Cd, Co, Ni or Cu; G=benzene)

New Hofmann-type complexes and clathrates of the forms M(piperidine)₂Ni(CN)₄ and M(piperidine)₂Ni(CN)₄·1.5G (M=Cd, Co, Ni or Cu; G=benzene) were prepared in powder form and their infrared and Raman spectra are reported. The spectral features suggest that these compounds are similar in structure to the Hofmann-type clathrates except for the copper compounds. The complex and clathrate of Cu have different spectral features in comparison with its analogues due to the Jahn-Teller effect.