Koordinationsverbindungen des β‐Methylmercapto‐äthylamins und des β‐Äthoxy‐äthylamins mit Salzen der 3d‐Elemente

“…Montmorillonites belong to the group of layer silicates. Their reactivity is mainly controlled by their large internal specific surface, the mean specific charge, and the nature of the interlayer-exchangeable cations. − Numerous publications have investigated the interaction of aniline and Cu(II) ions − proving the existence of labile weak complexes in aqueous solution. On the other hand, the interaction of aniline with montmorillonites at the gas−solid interface and in nonaqueous solutions is the subject of several publications.…”

Section: Introductionmentioning

confidence: 99%

Adsorption and Polymerization of Aniline on Cu(II)-Montmorillonite: Vibrational Spectroscopy and ab Initio Calculation

et al. 2000

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Batch adsorption experiments in the presence of oxygen were performed to study the interlayer reactions of aniline on Cu(II)-montmorillonite in aqueous solutions. At concentrations below a critical value of C C = 2.6 mmol dm-3 only a colored Cu(II)−aniline complex is formed, characterized by a stability constant of log(K assoc/dm3 mol-1) = 1.5. At concentrations beyond C c aniline polymerizes yielding a dark brown product, which is identified by two vibrational spectroscopy techniques, attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy and FT-Raman spectroscopy. Vibrational assignment of aniline, polyaniline, and the interlayer reaction products of aniline at Cu(II)-montmorillonite was achieved by a comparison of the band position and intensity observed in the ATR and FT-Raman spectra with wavenumbers and intensities (IR and Raman) from ab initio quantum-mechanical calculations. Density functional theory (DFT, B3LYP/6-31G*) has been used to calculate the geometry, frequencies, and intensities (IR and Raman) of aniline. The geometry and vibrational calculations of a four-ring unit (emeraldine base, EB) are believed to be a good representation of the polyaniline at Cu(II)-montmorillonite. The geometry of EB was fully optimized at the Hartree−Fock level of theory. The data of polyaniline presented suggest that IR and Raman data calculated ab initio on relatively short oligomers (quantum-mechanical oligomer approach) may provide valuable information regarding the interpretation of vibrational spectra of polymers. From the comparison of experiments and calculations, it is concluded that a catalytic/intercalation polymerization of aniline to polyaniline took place inside the interlayer of the Cu(II)-montmorillonite clay mineral.

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Die Komplexbildung von Kupfer(II)‐salzen mit Veresterungsprodukten der Äthanolamine

Uhlig¹,

Berner²

1966

J. Prakt. Chem.

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Ester des β‐Hydroxy‐äthylamins und des Bis‐(β‐hydroxy‐äthyl)‐amins bilden mit Kupfer(II)‐halogeniden kristalline 1,2‐Komplexe, während sich ihre Hydrochloride mit CuCl2 zu Tetrachlorocupraten(II) umsetzen. Aus Lösungen, die Tris‐(β‐phenyl‐carboxy‐äthyl)‐amin (TPÄ) und Kupfer(II)‐halogenide enthalten, kristallisieren Tri‐bzw. Tetrahalogenocuprate(II). Die erforderlichen Protonen werden in einer Nebenreaktion von Redoxcharakter geliefert. Partielle Veresterungsprodukte des Tris‐(β‐hydroxy‐äthyl)‐amins setzen sich mit Kupfer(II)‐salzen zu Koordinationsverbindungen von z. T. innerkomplexem Charakter um. Die Strukturen der dargestellten Verbindungen werden diskutiert.

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Koordinationsverbindungen des β‐Methylmercapto‐äthylamins und des β‐Äthoxy‐äthylamins mit Salzen der 3d‐Elemente

Cited by 15 publications

References 13 publications

Crystal and molecular structure of bis[.beta.-methylmercaptoethylamine]copper(II) diperchlorate

Crystal and molecular structure of bis[.beta.-methylmercaptoethylamine]copper(II) diperchlorate

Adsorption and Polymerization of Aniline on Cu(II)-Montmorillonite: Vibrational Spectroscopy and ab Initio Calculation

Die Komplexbildung von Kupfer(II)‐salzen mit Veresterungsprodukten der Äthanolamine

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