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  • Key words Solid state electrochemistry  (1)
  • Magnetic susceptibility  (1)
  • Organonickel(II) complexes  (1)
  • 1
    Electronic Resource
    Electronic Resource
    Solid state electrochemistry, X-ray powder diffraction, magnetic susceptibility, electron spin resonance, Mössbauer and diffuse reflectance spectroscopy of mixed iron(III)-cadmium(II) hexacyanoferrates (1999)
    Springer
    Journal of solid state electrochemistry 3 (1999), S. 264-276 
    Details
    ISSN: 1433-0768
    Keywords: Key words Solid state electrochemistry ; Mössbauer ; Magnetic susceptibility ; X-ray powder diffraction ; Iron(III)-cadmium(II) hexacyanoferrates
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Coprecipitates of CdII, KI and FeIII with hexacyanoferrate ions [Fe(CN)6]4− have been studied by solid-state electrochemistry (voltammetry of immobilized microparticles), magnetic susceptibility measurements, X-ray powder diffraction, electron spin resonance, Mössbauer and diffuse reflectance spectroscopy. Most suprisingly, all experimental results point to the formation of a continuous series of complex mixed phases without the formation of phase mixtures. Although CdII and FeIII ions differ too much in their ionic radii to allow the formation of simple substitution mixed hexacyanoferrates, they are capable of forming different kinds of complex insertion and substitution mixed crystals because of the zeolitic structure of both the iron and the cadmium hexacyanoferrate. Low cadmium concentrations can be found in the zeolitic cavities of iron hexacyanoferrate (Prussian blue), and they start to widen the lattice and facilitate, at higher concentrations, the direct substitution of high-spin iron(III) ions by cadmium ions. In cases of an excess of cadmium, the formation of cadmium hexacyanoferrate with iron(III) ions in the interstitials of the zeolitic structure is observed. These mixed phases show strong charge transfer bands in the visible range and have the appearance of “diluted” Prussian blue. For the first time, this indicates that the charge transfer between the carbon-coordinated low-spin iron(II) ions and the high-spin iron(III) ions can also occur when the latter are situated in the cavities of a host hexacyanoferrate. In Prussian blue the interstitial iron(III) ions are responsible for a very strong charge transfer interaction between the low-spin iron(II) ions and the nitrogen-coordinated high-spin iron(III) ions. Upon substitution of the very small amount of interstitial iron(III) ions in Prussian blue by potassium and cadmium ions the Kubelka-Munk function diminishes by more than 30%, indicating a tremendous decrease in iron(III)-iron(II) interaction.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s100080050157
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  • 2
    Electronic Resource
    Electronic Resource
    Schwefeldioxid als Ligand und Synthon. XII. Synthese und Reaktivität von Nickel(II)-Komplexen dreizähniger anionischer Liganden des Typs (C6H3{CH2NR1R2}2-2,6)- (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1931-1938 
    Details
    ISSN: 0044-2313
    Keywords: Organonickel(II) complexes ; SO2 coordination ; IR photoacoustic spectroscopy ; X-ray crystal structure of [NiBr{C6H3(CH2NR1R2)2-2,6}] ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Sulfur Dioxide as Ligand and Synthon. XII. Synthesis and Reaction Behaviour of Nickel(II) Complexes with Terdendate Anionic Ligands of the Type (C6H3{CH2NR1R2}2-2,6)-Organonickel(II) complexes of the type [NiX{C6H3(CH2NR1R2)2-2,6}] (X = halide OH2+/CF3SO3-; R1=R2=Et 1; R1=R2=i—Pr 2; R1 = Me, R2 = Cy 3; (NR1R2) = piperidino 4; (NR1R2) = pyrrolidino 5) are described. 1H and 13C NMR and UV/Vis spectra were recorded, and the X-ray crystal structure of 1 a (X = Br) was determined. This complex crystallizes orthorhombically in the space group Pbca with a = 1 335.8(2) pm, b = 1 903.3(3) pm, c = 1 365.4(3) pm and Z = 8, and has an approximately square-planar geometry. 4 and 5 show a reversible binding of SO2 which has been detected by means of IR photoacoustic spectroscopy. The reactions of 1-5 with CS2 and PhNSO are discussed.
    Notes: Organonickel(II)-Komplexe des Typs [NiX{C6H3(CH2NR1R2)2-2,6}] (X = Halogen, OH2+/CF3SO3-; R1=R2=Et 1; R1=R2=i—Pr 2; R1 = Me, R2 = Cy 3; (NR1R2) = piperidino 4; (NR1R2) = pyrrolidino 5) werden beschrieben. Die Charakterisierung erfolgte mit Hilfe der 1H— und 13C-NMR- sowie der UV/Vis-Spektroskopie. Von 1 a (X = Br) wurde die Kristallstruktur bestimmt. Dieser Komplex kristallisiert orthorhombisch in der Raumgruppe Pbca mit a = 1 335,8(2) pm, b = 1 903,3(3) pm, c = 1 365,4(3) pm und Z = 8, er besitzt eine annähernd quadratisch-planare Geometrie. 4 und 5 vermögen SO2 reversibel zu fixieren, was durch die IR-Photoakustik-Spektroskopie nachweisbar ist. Die Reaktionen von 1-5 mit CS2 und PhNSO werden diskutiert.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19936191118
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