Über Komplexe Fluoride des zweiwertigen Palladiums

On Complex Fluorides of Divalent Palladium For the first time single crystals of the new compounds RbPdPdF₅, KPdPdF₅, and K₂CsPdF₅ have been obtained. Orange brown RbPdPdF₅ crystallizes orthorhombic, space group Imma–D_2h²⁸ (No. 74) with a = 633.6(1) pm, b = 765.5.(1) pm, c = 1067.5(1) pm and Z = 4 and is isotypic with CsPdPdF₅ [1]. Structure related KPdPdF₅ (also orange brown) crystallizes orthorhombic too, but in space group Pnma–D_2h¹⁶ (No. 62) with a 614.12(9) pm, b = 748.7(1) pm, c = 1065.0(2) pm and Z = 4. K₂CsPdF₅, light yellow, crystallizes tetragonal with a = 736.3(1) pm, c = 628.0(1) pm, Z = 2, and is isotypic with Rb₂CsPdF₅ (space group P4/mbm? D_4h⁵ Nr. 127), an ordered structure variant of the Rb₃PdF₅-Type [1].     

Über Fluoride des zweiwertigen Eisens. Zum Aufbau von CsFeF3

Fluorides with Divalent Iron: On the Structure of CsFeF₃ By ?reaction with the wall”? according to 3 CsF + 2 FeF₃ + Fe_wall = 3 CsFeF₃ we obtained for a first time colourless single crystals of CsFeF₃. The lattice constants were redetermined with a = 616.39(6) pm, c = 1487.02(15) pm (Four circle diffractometer PW 1100, AgK$ \bar \alpha $, R = 4.33%, R_w = 2.79%). CsFeF₃ crystallizes isotypic to BaTiO₃ in the space group P6₃/m mc. Parameters see text. The Madelung Part of Lattice Energy, MAPLE, and the ?Effective Coordination Numbers”?, ECoN, via the ?Mean Fictive Ionic Radii”?, MEFIR, are calculated and discussed.     

Über Fluoride des zweiwertigen Eisens: Cs7Fe4F15

Concerning the Cleavage of Si? C Bonds in Si-methylated Carbosilanes The chances for the cleavage of Si? Me bonds (Me ? CH₃) and Si? C? Si bonds in their molecular skeletons using ICl or ICl/AlBr₃ are examined in 13 carbosilanes; i. e. (Me₂Si? CH₂)₃ 1 , 1,3,5,7-tetramethyl-1,3,5,7-tetrasilaadamantane 2 , (Me₃Si? CH₂)₂SiMe₂ 3 , HC(SiMe₃)₃ 4 , the 1,3,5,7-tetrasilaadamantane. carrying bhe ? CH₂? SiMe, group at one Si atom 5 , the 1,3,5-trisilacyclohexane, carrying the ? CH₂? SiNe₃ group 6 , three derivatives of the 1,3,5-trisilacyclohexane, carrying SiMe₃ groups at skeletal C atoms 7 , 8 , 9 , three derivatives of the 1,3,5-trisilacyclohexane, carrying CH₃, groups at skeletal C atoms 10 10, 11 , 12 and 13 , derived from (Me₂Si? CH₂)₃ having one ?CBr₂ group. Using ICl one Me group at each Si atom in 1 can be split off successively, finally yielding (ClMeSi? CH₂)₃. 2 is transformed to the Si-chlorinated 1,3,5,7-tetrasilaadamantane. 3 , treated with ICl yields (ClMeSi? CH₂)₂SiMeCl, as 4 forms HC(SiMe₂Cl)₃. Higher chlorinated compounds can be obtained by using ICl and AlBr₃ in catalytic amounts. Thus 1 leads to (Cl₂Si? CH₂)₃, no ring-opening is observed. However, in the reaction of 1 with HBr/AlBr₃ bromination at the Si atoms and ring-opening (ratio 1:1) proceed coincidently. The reaction of either 3 or (ClMe₂Si? CH₂)₂SiMeCl with ICl/AlBr₃ leads to (Cl₂MeSi? CH₂)₂SiCl₂, and (Me₃Si)₂CH₃ forms (Cl₂MeSi? )₂CH₂ similarly. The ? CH₂? SiMe₃ group in 5 and 6 is not cleaved off by ICl; the introduction of a Cl group at each Si atom is observed instead. Furthermore, 6 undergoes cleavage (≈8%) of the Si? C ring adjacent to the chain-substituted Si atom [formation of ClMe₂Si? (CH₂? SiMeCl)₂CH₂? SiMe₂? CH₂Cl]. 7 , 8 , 9 (having the ? SiMe₃ group at the C atoms) react with ICl by splitting off one Si? Me group from each Si atom. In 7 we also observe the ring-opening to an amount of ≈25% [formation of (ClMe₂Si)CH₂? SiMeCl? CH₂? SiMe₂? CH₂Cl]. In ₈ (having two CH(SiMe₃) groups the ring-opening reaction is reduced to about 5% [formation of ClMe₂? CH(SiMe₂Cl)? SiMeCl? CH(SiMe₂Cl)? SiMe₂? CH₂Cl], while in 9 (having three CH(SiMe₃) groups) it is not found at all. In 10 , 11 , 12 (having the CH₃ group at the C atoms) ICl substitutes one Me group (formation of SiCl) at each Si atom (no ring-opening). The CBr₂ group reduces the reactivity of 13 towards ICl. Only the split-off of one Me group at the Si atom in para-position to the CBr₂ group is observed. Using ICl/AlBr₃ higher chlorinated derivatives are obtained (no ring-opening). Most of the mentioned compounds were identified via their Si? H-containing derivatives, thus facilitating the chromatographic separation as well as the ¹H-NMR-spectroscopic investigations.     

Über Fluoride des zweiwertigen Eisens: Ba2[Fe3F10]

On the Knowledge of Ba₂[Fe₃F₁₀] For the first time colourless single crystals of Ba₂Fe₃F₁₀ have been prepared by reduction of a mixture of 3 BaF₂/7 FeF₃ in a Fe-tube (reaction with the wall 750°C, 60 d). Ba₂Fe₃F₁₀ crystallizes in the monoclinic spcgr. P2₁/c with a = 788.3(1), b = 623.0(1), c = 1868.0(3) pm, β = 111.79(1)º, Z = 4. (Fourcircle diffractometer PW 1100, Fa. Philips, MoKα, 2383 of 2383 I₀(hkl), R = 8.1%, R_w = 4.1%, parameters see in the text). The Madelung Part of Lattice Energy, MAPLE, is calculated and discussed.     

Trennung von einwertigen und zweiwertigen Phenolen mittels Gaschromatographie

Ohne Zusammenfassung     

Über s-Triazinium-Salze und Additionsverbindungen des s-Triazins

Several unknown salts of s-triazine were prepared by different methods and the IR spectra of most of these salts were assigned. When s-triazine was reacted with HCl or HBr, mixtures were obtained which consisted of s-triazinium-monohalogenides and products with higher contents of hydrohalogenides. When s-triazine was reacted with HJ, a product C₃H₃N₃ · 3 HJ was obtained. The IR spectra of this compound and of the corresponding compound with DJ were taken to interprete the structure. Addition compounds of s-triazine with several ansolvo-acids were produced in which one or two ansolvo-acid molecules were bound to one molecule of s-triazine. The IR spectra of some of said addition compounds were assigned. Moreover, an adduct of bromine and s-triazine, C₃H₃N₃ · Br₂, was prepared.     

Über Silicid- und Germanidchalkogenide des Thoriums

On Thorium Silicide and Germanide Chalcogenides The compounds ThSiS, ThSiSe, ThSiTe, ThGeS, ThGeSe, and ThGeTe were synthetized from the elements at temperatures ranging from 800 to 1050°C. For structural X-ray investigation single crystals of the compound ThGeS were grown. ThGeS is tetragonal, space group I4/mmm with a = 3.9411(7), c = 17.1395(40) Å, and Z = 4. In order to refine the structure parameters intensity measurements were carried out by means of a four-circle single crystal diffractometer. By indexing the Debye-Scherrer diagrams the remaining ternary thorium chalcogenides were proved to be isostructural with ThGeS. This structure type is identical with the anti-Ti₂Bi-type structure and closely related to the PbFCl structure in the sense of a transposition structure. The interatomic distances, the relations to comparable structures and possible reasons for the formation of the anti-Ti₂Bi-type structure by ternary chalcogenides of the actinides are discussed.     

Über Polyphosphide des Lanthans und Cers

The systems LaP/P and CeP/P were investigated. Polyphosphide phases with the compositions LaP_1.6–2.5 (A), LaP_3.5–5.3(B), LaP_5.8–9.0(C) and LaP_6.5–8.9(D), respectively, as well as CeP_1.7–2.4 (A′), CeP_3.5–6.5(B) CeP_6.5–9.0(C) and were found. The phases B and C of lanthanum and cerium are isotypic, but not the phases A and A′. The phases C and D of lanthanum are different modifications with approximately equal homogenity ranges.     

Über Tetraiodomercurate des Calciums und Strontiums

On Tetraiodomercurates of Calcium and Strontium Tetraiodomercurates MHgI₄ · 8 H₂O (M ? Ca, Sr) as yellow crystals are obtainable by crystallization from aqueous solutions. Both compounds are not isotype in spite of consisting isolated [M(OH₂)₈] cations and tetrahedral [HgI₄] anions which are cubic closed packed. In the structure of the tetragonal CaHgI₄ · 8 H₂O (a = 13.972(3) Å; c = 18.155(4) Å; Z = 8; P4₂/mbc) are dodecahedral [Ca(OH₂)₈] cations, but antiprismatic [Sr(OH₂)₈] groups in the orthorhombic compound SrHgI₄ · 8 H₂O (a = 9.616(3) Å; b = 10.610(3) Å; c = 17.731(4) Å; Z = 4; Pcmn). The relations between both structure concerning a tetragonal “Aristotype” are discussed.     

Über Triphosphorsäurederivate des Cyanamids und des Harnstoffs

Triphosphoric Acid Derivatives of Cyanamide and Urea Cyanamidotriphosphate, P₃O₉NCN^5? ( I ), is obtained by ring opening reaction of the cyclotriphosphate ion, P₃O₉^3?, by cyanamide in alkaline solution. As a pseudochalcogeno-substituted triphosphate, I has similar properties like the triphosphate, P₃O₁₀^5? (Ca²⁺ sequestering; behaviour on acidimetric titration; X-ray powder diffraction of the sodium salt hydrates). In acidic solution I decomposes forming ureidotriphosphate with the anion P₃O₉NHCONH₂^4? ( II ) which cannot be directly obtained from cyclotriphosphate and urea. II is characterized by its chemical analysis, by paper chromatography, by its behaviour in acidic solution and by its IR and ³¹P-NMR spectra. Solid salts of I and II are prepared and the data of their Guinier diagrams are communicated.     

Über Chloridsilicate des Calciums,Strontiums und Bariums

On Chloride Silicates of Calcium, Strontium, and Barium Alkaline earth chloride silicates are synthesized by heating of mixtures of CaCO₃, SrCO₃ or BaCO₃, and SiO₂ with different molar ratios in the melt of the relating alkaline earth chloride. They can be separated from an excess of chloride by methanol extraction. The structures of their silicate anions were investigated by the molybdate method and paper chromatographic separation. The compounds Sr₅[SiO₄]Cl₆, Sr₅[Si₂O₇]Cl₄, and Sr₈[Si₄O₁₂]Cl₈, hitherto unknown, were synthesized and compared with the compounds of calcium and barium in regard of their chloride contents, silicate anion structure and crystal structure.     

Über Chalkogenidhalogenide des Kupfers

Nine ternary chalcogenidehalides of copper could be synthesized under hydrothermal conditions from the resp. hydrogen halide solutions. They belong to the pseudobinary systems, formed between selenium and tellurium and the resp. Cu^I halide. In the selenium systems exist: CuISe₃, rhombohedral; CuBrSe₃, orthorhombic, and CuClSe₂, monoclinic. Two homologous series of tellurium compounds exist: CuXTe, tetragonal, and CuXTe₂, monoclinic (X ? Cl, Br, I). Thermodynamic data could be obtained for the selenium compounds using the Knudsen effusion method. The samples exhibit a temperature independant diamagnetism. All compounds can also be synthesized by reaction of stoichiometric amounts of Cu^I halide and selenium (300°C) or tellurium (350°C). The corresponding thiohalides could not be observed.     

Über Oxarsolane und Thioarsolane

Elimination of HCl from 1,3-propanoldichloroarsine, HOC₃H₆AsCl₂, yields 2-chloro-1,2-oxarsolane. Hydrolysis in the presence of triethylamine gives bis-1,2-oxarsolanyloxide. Bis-1,2-thioarsolanyl-sulphide is obtained from 1,3-chloropropyl-arsenicsulphide, (ClC₃H₆AsS)₃, by interaction with thiourea and decomposition of the intermediate thiuronium salt. Reaction with AsCl₃ yields the 2-chloro-1,2-thioarsolane which may be hydrolized to bis-1,2-thioarsolanyl-oxide.     

Über die Reindarstellung des Bromchlorids und dessen Verhalten in Acetonitril

The Preparation of Pure Bromine Chloride and on its Behaviour in Acetonitrile. Pure bromine chloride has successfully been prepared from bromine and chlorine. The bromine was quantitatively chlorinated in solution of difluordichlormethane with a large exess of chlorine at ?79°C under irradiation with U.V. light. The bromine chloride so obtained was removed from equilibrium by precipitation under cooling to ?120 to ?110°C. The solvent and the exess chlorine then were destillad at the same temperature under high vacuum, the system being detached from vacuum as soon as the residue was dry. Using a temperature difference of 1°, the orange-coloured crystalline powder could bee sublimated at ?79°C, the resulting beautiful, orange-coloured crystals (m. p. ?56,5°C) being completely stable in a trap at ?79°C. In acetonitrile as solvent, bromine chloride is stable even at room temperature because of the formation of an adduct with the solvent. In these solutions exists the ionic equilibrium 2 BrCl_solv?Br + BrCl.