Darstellung und spektroskopische Charakterisierung der Persulfoniumsalze (CH3)(CF3)SF3+SbF6− und (CH3)(CF3)2SF2+SbF6− und Kristallstruktur von CF3SF2+SbF6−

Preparation and Spectroscopic Characterization of the Persulfonium Salts (CH₃)(CF₃)SF₃⁺SbF₆^? and (CH₃)(CF₃)₂SF₂⁺SbF₆^? and Crystal Structure of CF₃SF₂⁺SbF₆^? [1] . The preparation of the persulfonium salts (CH₃)(CF₃)SF₃⁺SbF₆^? and (CH₃)(CF₃)₂SF₂⁺SbF₆^? by methylation of the sulfuranes CF₃SF₃ and (CF₃)₂SF₂ with CH₃OSO⁺SbF₆^? in liquid SO₂ is reported. The thermolabile compounds are characterized by IR, Raman, ¹H, ¹³C, and ¹⁹F NMR spectroscopy. CF₃SF₂⁺SbF₆^? crystallizes in the space group C2/c with a=16.889(8) Å, b=7.261(4) Å, c=13.416(7) Å, β=91.08° with 8 formula units per unit cell at 167 K. Cations and anions are connected via short SF contacts forming a Ψ-octahedral surrounding of the central S atom which is in close analogy to the already known CF₃SF₂⁺AsF₆^?.     

Darstellung und Charakterisierung von Phthalocyanin-π-Kation-Radikalen von H+, Mg2+ und Cu2+

Preparation und Characterization of Phthalocyanine-π-Cation-Radicals of H⁺, Mg²⁺, and Cu²⁺ The preparation of phthalocyanine-π-cation-radicals (Pc(?1)) of H⁺, Mg²⁺, Cu²⁺ is described. MgClPc(?1) and Cu(NO₃)Pc(?1) · HNO₃ are isolated as stoichiometrically pure, stable redbrown solids. Contrary to the phthalocyanines(?2) (Pc(?2)) these are very soluble with redviolet colour in organic solvents in the presence of R? COOH (R ? H, CF₃, CCl₃). The electronic absorption absorption spectra (UV-VIS) are remarkably solvent-dependent. This solvent effect is due to a reversible radical association. Monomeric radical species exist in nonpolar (CH₂Cl₂), dimeric in polar solvents (CH₃NO₂, C₂H₅OH). The UV-VIS, infrared (IR), and resonance-raman (RR) spectra of MgClPc(?1) and Cu(NO₃)Pc(?1) · HNO₃ are discussed and compared with the analogoues spectra of MgPc(?2) · 2 H₂O and MgPc(?2) · HCl. Although there are only minor differences in the chemical composition and the electronic structure the spectroscopic data vary significantly for every complex. Especially the IR spectrum is suitable for a quick demonstration of the π-cation-radicals. The diagnostic bands are at ca. 1350 and 1450 cm^?1.     

Strukturchemische und impedanzspektroskopische Untersuchungen an Mg2+-stabilisierten Na+/Pr3+-β″-Al2O3-Kristallen

Structural Chemistry and Impedance Spectroscopy of Mg²⁺ stabilized Na⁺/Pr³⁺-β″-Aluminas The structure with the ionic distribution in the conduction planes of a Pr³⁺-exchanged Mg²⁺ stabilized Na⁺-β″-alumina crystal, composition determined by electron microprobe analysis to Na_1.19Pr_0.13Mg_0.49Al_10.49O₁₇ (degree of exchange ξ = 25%, related to Na⁺ content), has been investigated by single crystal X-ray diffraction methods at room temperature (R3 m, Z = 3, a = 561.8(2) pm, c = 3 361.5(11) pm). Pr³⁺ is slightly shifted in the ab-plane from the centrosymmetric 9 d (mO) into a 18 h site. Na⁺ occupies 18 h as well as 6 c (BR) positions. Ionic conductivity data of Mg²⁺ stabilized Na⁺/Pr³⁺-β″-Al₂O₃ crystals with varying degree of exchange determined by impedance spectroscopy are given in an Arrhenius diagram. With growing Pr³⁺ content the conductivity σ decreases with increasing activation energy.     

Schwingungsspektroskopische Untersuchungen an Trimethylphosphonium-Kationen (CH3)3PX+ (X = H,D) und Kristallstrukturen von (CH3)3PD+SbCl6− und (CH3)3PCl+SbCl6−

Vibrational Spectra of Trimethylphosphonium Cations (CH₃)₃PX⁺ (X = H, D) and Crystal Structures of (CH₃)₃PD⁺SbCl₆^? and (CH₃)₃PCl⁺SbCl₆^? The trimethylphosphonium salts (CH₃)₃PX⁺SbCl₆^? (X = H, D) and (CH₃)₃PH⁺MF₆^? (M = As, Sb) are prepared and characterized by vibrational and NMR spectroscopy (¹H, ³¹P, ¹³C). In addition the crystal structures of (CH₃)₃PD⁺SbCl₆^? and (CH₃)₃PCl⁺SbCl₆^? are reported. (CH₃)₃PD⁺SbCl₆^? crystallizes in the orthorhombic space group Pnma with a = 1555(1) pm, b = 753.1(8) pm, c = 1166(1) pm Z = 4. (CH₃)₃PCl⁺SbCl₆^? crystallizes triclinic in the space group P1 with a = 704.6(4) pm, b = 729.5(3) pm, c = 1391.1(7) pm, α = 89.57(4)°, b? = 88.04(4)°, γ = 74.98(4)° and Z = 2.     

Über die Kristallstrukturen von CH3PF2H+AsF6− und CH3PF2H+SbF6− und eine einfache Darstellung von CH3PF2

On the Crystal Structures of CH₃PF₂H⁺AsF₆^? and CH₃PF₂H⁺SbF₆^? and a simple Method for Preparation of CH₃PF₂ A simple method for preparation of CH₃PF₂ from CH₃PCl₂ is reported. The phosphonium salts CH₃PF₂H⁺MF₆^? are obtained by the reaction of CH₃PCl₂ with superacidic systems HF/MF₅ (M = As, Sb). CH₃PF₂H⁺SbF₆^? crystallizes in the space group P1 with a = 548.4(4) pm, b = 695.5(8) pm, c = 960.2(9) pm, α = 94.68(5)°, β = 97.19(6)°, γ = 94.41(6)° and Z = 2. CH₃PF₂H⁺SbF₆^? crystallizes in P1 with a = 554.3(3), b = 724.2(4), c = 970.4(5), α = 94.73(4)°, β = 96.14(5)°, γ = 95.30(4)°.     

Neue Fluorozirconate und ‐hafnate mit V2+ und Ti2+

New Fluorozirconates and ‐hafnates with V²⁺ and Ti²⁺ During investigations of the systems MF₂/KF/MF₄ e. g. MF₂/NaF/MF₄ (M²⁺ = Ti²⁺, V²⁺, M⁴⁺ = Zr⁴⁺, Hf⁴⁺) we obtained blue crystals of VZrF₆, VHfF₆, KVZrF₇, blue‐green crystals of NaVHf₂F₁₁, yellow crystals of TiHfF₆ and NaTiHf₂F₁₁, and yellow to rubyred crystals of TiZrF₆, respectively. According to single crystal data, VZrF₆ VHfF₆ and TiZrF₆ crystalizes in the ordered ReO₃‐type (cubic, Fm3m, a = 812,1(5), 804,2(8), and 821,0(2) pm, Z = 4). TiHfF₆ crystalizes in a high‐temperature‐modification (cubic, ReO₃‐type, Pm3m, a = 392,3(2) pm, Z = 2). KVZrF₇ is isotyic to KPdZrF₇ (orthorhombic, Pnna, a = 1109,8(6), b = 788,0(7), c = 648,0(15) pm, Z = 4). NaTiHf₂F₁₁ and NaVHf₂F₁₁ crystalizes monoclinic (C2/m, a = 910,5(7), b = 675,9(7), c = 773,6(5) pm, β = 116,10(6)° and a = 917,7(5), b = 685,7(5), c = 752,4 pm, β = 118,28(1)°, Z = 2, respectively) and are also isotypic to already known AgPdZr₂F₁₁.     

Optische Untersuchungen an PrCl3 und Pr3+ -dotierten Selten-Erd-Trichloriden

Optical Investigations on PrCl₃ and Pr³⁺-doped Rare Earth Trichlorides The ground state crystal field splitting of Pr³⁺ in PrCl₃ and the doped compounds CeCl₃: 1% Pr³⁺ and EuCl₃: 1% Pr³⁺ was investigated by fluorescence techniques and interpreted by angular overlap model calculations. The dependence of the spectra on the host crystal structure is discussed.     

Darstellung und spektroskopische Charakterisierung von Fluortrichlor-arsoniumhexafluoroarsenat,AsFCl3+AsF6−

Preparation and Spectroscopic Characterization of Fluorotrichloroarsonium Hexafluoroarsenate, AsFCl₃⁺AsF₆^? The mixed halide pniktide cation AsFCl₃⁺ is prepared by oxidative fluorination of AsCl₃ with XeF⁺ AsF₆^?. AsFCl₃⁺ AsF₆^? is characterized by IR, Raman, and ¹⁹F-NMR spectroscopy.     

Na3AsSe3 und K3AsSe3 – Darstellung und Kristallstruktur

Na₃AsSe₃ and K₃AsSe₃ – Synthesis and Crystal Structure The compounds Na₃AsSe₃ and K₃AsSe₃ were synthesized by heating mixtures of As₂O₃ and the respective alkalicarbonate in a stream of hydrogen saturated by selenium at 750 °C. The structures were determined from X-ray single-crystal diffractometer data. Both compounds crystallize isostructural with Na₃AsS₃, space group P2₁3, Z = 4, lattice constants a = 8,925 (1) Å for Na₃AsSe₃ and a = 9,710(1) Å for K₃AsSe₃.