Kryometrische Untersuchungen. IV. Lösungen von oxidischen Mo6+- und Cr6+-Verbindungen in geschmolzenem K2Cr2O7 und KNO3

The depression of freezing point of molten K₂Cr₂O₇ and KNO₃ as solvents was measured after addition of small concentrations of the following compounds: to K₂Cr₂O₇: MoO₃, CrO₃, (NH₄)₂CrO₄, K₂MoO₄, Na₂MoO₄, Li₂MoO₄, and Na₂Mo₂O₇, respectively; to KNO₃: CrO₃, (NH₄)₂Cr₂O₇ K₂Cr₂O₇, K₂CrO₄ and MoO₃, (NH₄)₆(Mo₇O₂₄) · 4 H₂O, K₂Mo₂O₇, K₂MoO₄, Na₂MoO₄ and Li₂MoO₄, respectively. It could be concluded from the measured values of the freezing point depression if a reaction between solvent and solute took place.     

Synthesis of Inorganic Structural Isomers By Diffusion‐Constrained Self‐Assembly of Designed Precursors: A Novel Type of Isomerism

The structure of precursors is used to control the formation of six possible structural isomers that contain four structural units of PbSe and four structural units of NbSe₂: [(PbSe)_1.14]₄[NbSe₂]₄, [(PbSe)_1.14]₃[NbSe₂]₃[(PbSe)_1.14]₁[NbSe₂]₁, [(PbSe)_1.14]₃[NbSe₂]₂[(PbSe)_1.14]₁[NbSe₂]₂, [(PbSe)_1.14]₂[NbSe₂]₃[(PbSe)_1.14]₂[NbSe₂]₁, [(PbSe)_1.14]₂[NbSe₂]₂[(PbSe)_1.14]₁[NbSe₂]₁[(PbSe)_1.14]₁[NbSe₂]₁, [(PbSe)_1.14]₂[NbSe₂]₁[(PbSe)_1.14]₁[NbSe₂]₂[(PbSe)_1.14]₁[NbSe₂]₁. The electrical properties of these compounds vary with the nanoarchitecture. For each pair of constituents, over 20 000 new compounds, each with a specific nanoarchitecture, are possible with the number of structural units equal to 10 or less. This provides opportunities to systematically correlate structure with properties and hence optimize performance.     

On precipitation effects of aluminum,lanthanum, iron (III), and thorium phosphates

Summary Typical precipitation curves of various metal phosphates have been obtained using the turbidimetric technique. The following systems have been investigated: Al(NO₃)₃-K₃PO₄, Al(NO₃)₃-KH₂PO₄, Al(NO₃)₃NaH₂PO₄, FeCl₃-K₃PO₄, FeCl₃-(NH₄)₂HPO₄, FeCl₃K₂HPO₄, FeCl₃-KH₂PO₄, FeCl₃-NaH₂PO₄, La(NO₃)₃K₃PO₄,La(NO₃)₃-K₂HPO₄,La(NO₃)₃-KH₂PO₄,La(NO₃)₃NaH₂PO₄ and Th(NO₃)₄-K₂HPO₄. Typical precipitation curves indicated concentration ranges of phosphate precipitation and of complex solubility.

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Zusammenfassung Typische F?llungskurven verschiedener Metallphosphate, die mittels Trübungsmessungen erhalten wurden, wurden graphisch dargestellt. Die folgenden Systeme wurden untersucht: Al(NO₃)₃-K₃PO₄,Al(NO₃)₃KH₂PO₄, Al(NO₃)₃-NaH₂PO₄, FeCl₃-K₃PO₄, FeCl₃(NH₄)₂HPO₄, FeCl₃-K₂HPO₄, FeCl₃-KH₂PO₄, FeCl₃NaH₂PO₄, La(NO₃)₃-K₃PO₄, La(NO₃)₃-K₂HPO₄, La(NO₃)₃-KH₂PO₄, La(NO₃)₃-NaH₂PO₄ und Th(NO₃)₄K₂HPO₄. Typische F?llungskurven zeigten Konzentrationsgebiete, in welchen die Metallphosphate gef?llt werden, sowie Konzentrationen, die zur Komplexbildung führten.

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Supported in part by the U.S. Army Research Office, Contract No. DA-ORD-10.     

Acetylenic derivatives of metal carbonyls of the triad Fe,Ru, Os—XI Mass spectra of some binuclear complexes

The mass spectra of the following acetylenic derivatives of iron, ruthenium and osmium carbonyls are reported: the iron compounds Fe₂(CO)₆[C₂(C₆H₅)s₂]₂, Fe₂(CO)₆[C₂(CH₃)₂]₂ and Fe₂(CO)₆[C₂(C₂H₅)₂]₂, the ruthenium compounds Ru₂(CO)₆[C₂(C₆H₅)₂]₂, and Ru₂(CO)₆[C₂(CH₃)₂]₂ and the osmium compounds Os₂(CO)₆[C₂(C₆H₅)₂]₂, Os₂(CO)₆[C₂HC₆H₅]₂ and Os₂(CO)₆[C₂(CH₃)₂]₂. Iron compounds exhibit breakdown schemes where binuclear, mononuclear and hydrocarbon ions are present. On the other hand, ruthenium and osmium compounds fragment in a similar way and give rise to singly and doubly charged binuclear ions. Phenylic derivatives of ruthenium and osmium also give weak triply charged ions. The results are discussed in terms of relative strengths of the metal-metal and metal-carbon bonds.     

Chemie polyfunktioneller liganden LXIII. Adamantankäfigverbindungen mit den heteroelementen arsen,stickstoff und silizium

The reaction of 1,1,1-tris(diiodarsinomethyl)ethane, CH₃C(CH₂AsI₂)₃ (I), with i-C₃H₇NH₂, n-C₄H₉NH₂, C₆H₅NH₂, p-CH₃C₆H₄NH₂ and [(CH₃)₃Si]₂NH in the presence of (C₂H₅)₃N as auxiliary base in THF gives the adamantane cage compounds CH₃C(CH₂AsNC₃H₇)₃ (III), CH₃C(CH₂AsNC₄H₉)₃ (IV), CH₃C(CH₂AsNC₆H₅)₃ (V), CH₃C(CH₂AsNC₆H₄CH₃)₃ (VI) and CH₃C[CH₂AsNSi(CH₃)₃]₃ (VII). VII is also obtained in the reaction of I with NaN[Si(CH₃)₃]₂. The by-product (CH₃)₃SiO(CH₂)₄I (VIII) could be isolated in both syntheses of VII. All compounds have been characterized by mass spectrometry and infrared, Raman and ¹H NMR spectroscopy.     

Beiträge zur Chemie von Phosphorverbindungen mit Adamantanstruktur. XI. Über Darstellung und Eigenschaften von Phosphoroxidsulfiden der allgemeinen Formel P4O10−nSn (n = 2−9)

Contributions to the Chemistry of Phosphorus Compounds with Adamantane-like Structure. XI. Preparation and Properties of Phosphorus Oxide Sulfides of the General Formula P₄S_10?n S_n (n = 2?9) The reaction of P₄O₁₀ with P₄S₁₀ yields a mixture of phosphorus oxide sulfides of the general formula P₄O_10?nS_n. Depending on the molar ratio P₄O₁₀: P₄S₁₀ in the starting product different amounts of the individual phosphorus oxide sulfides occuring in this reorganization product are formed. Besides the well-known P₄O₆S₄ the compounds P₄O₇S₃, P₄O₅S₅, P₄O₄S₆, P₄O₃S₇, P₄O₂S₈, and P₄OS₉ occuring for the first time were obtained by fractional distillation or crystallization. The compound P₄O₈S₂ was identified by N.M.R. spectroscopy.     

Mass spectra of organometallic compounds—VII; Organonitrogen derivatives of metal carbonyls

The positive-ion mass spectra of the following organonitrogen derivatives of metal carbonyls are discussed: (i) The compounds NC₅H₄CH₂Fe(CO)₂C₅H₅, NC₅H₄CH₂COMo(CO)₂C₅H₅, NC₅H₄CH₂W(CO)₃C₅H₅, NC₅H₄CH₂COMn(CO)₄, C₅H₁₀NCH₂CH₂Fe(CO)₂C₅H₅, (CH₃)₂NCH₂CH₂COFeCOC₅H₅ and (CH₃)₂NCH₂CH₂COMn(CO)₄ obtained from metal carbonyl anions and haloalkylamines, (ii) The isocyanate derivative C₅H₅Mo(CO)₃CH₂NCO; (iii) The arylazomolybdenum derivatives RN₂Mo(CO)₂C₅H₅ (R ? phenyl, p-tolyl, or p-anisyl); (iv) The compound (C₆H₅N)₂COFe₂(CO)₆ obtained from Fe₃(CO)₁₂ and phenyl isocyanate; (v) The N,N,N′,N′-tetramethylethylenediamine complex (CH₃)₂NCH₂CH₂N(CH₃)₂W(CO)₄. Further examples of eliminations of hydrogen, CO, and C₂H₂ fragments were noted. In addition evidence for the following more unusual processes was obtained: (i) Elimination of HCN fragments from the ions [NC₅H₄CH₂MC₅H₅]⁺ to give the ions [(C₅H₅)₂M]⁺ (M ? Fe, Mo and W); (ii) Conversion of C₅H₅Mo(CO)₃CH₂NCO to C₅H₅Mo(CO)₂CH₂NCO within the mass spectrometer; (iii) Elimination of N₂ from [RN₂MoC₅H₅]⁺ to give [RMoC₅H₅]⁺; (iv) Novel eliminations of HNCO, FeNCO, and C₆H₅NC fragments in the mass spectrum of (C₆H₅N)₂COFe₂(CO)₆; (v) Facile dehydrogenation of the N,N,N′,-N′-tetramethylethylenediamine ligand in the complex (CH₃)₂NCH₂CH₂N(CH₃)₂W(CO)₄.     

The chemistry of chromyl fluoride III. Reactions with inorganic systems

Reactions of CrO₂F₂ with MF or MF₂ gave the corresponding M₂CrO₂F₄ and MCrO₂F₄ fluorochromates. With the Lewis Acids (SO₃, TaF₅, SbF₅) and (CF₃CO)₂O known and new chromyl compounds [CrO₂(CF₃COO)₂, CrO₂(SO₃F)₂, CrO₂FTaF₆, CrO₂FSbF₆, CrO₂FSb₂F₁₁] were produced. Chromyl fluoride and inorganic salts (CF₃COONa and NaNO₃) produced the following complexes - Na₂CrO₂F₂(CF₃COO)₂ and Na₂CrO₂F₂(NO₃)₂. Unusual solid products were obtained with CrO₂F₂ and NO, NO₂, SO₂.A new method of preparing CrO₂F₂ is also presented.     

Reaktionen von R4Sb2 (R = Me,Et) mit (Me3SiCH2)3M (M = Ga,In) und Kristallstrukturen von [(Me3SiCH2)2InSbMe2]3 und [(Me3SiCH2)2GaOSbEt2]2

Reactions of R₄Sb₂ (R = Me, Et) with (Me₃SiCH₂)₃M (M = Ga, In) and Crystal Structures of [(Me₃SiCH₂)₂InSbMe₂]₃ and [(Me₃SiCH₂)₂GaOSbEt₂]₂ The reaction of (Me₃SiCH₂)₃In with Me₂SbSbMe₂ gives [(Me₃SiCH₂)₂InSbMe₂]₃ ( 1 ) and Me₃SiCH₂SbMe₂. [(Me₃SiCH₂)₂GaOSbEt₂]₂ ( 2 ) is formed by the reaction of (Me₃SiCH₂)₃Ga with Et₂SbSbEt₂ and oxygen. The syntheses and the crystal structures of 1 and 2 are reported.     

The synthesis and structure of triphenylsiloxycyclotriphosphazenes

The triphenylsiloxy-substituted cyclotriphosphazenes, N₃P₃Cl₅OSiPh₃, gem-N₃P₃Cl₄(OSiPh₃)₂, N₃P₃(OSiPh₃)₆, and N₃P₃(OPh)₅OSiPh₃, have been prepared. The synthesis of gem-N₃P₃Cl₄(OSiPh₃)₂ involves the reaction of (NPCl₂)₃ with Ph₃SiONa to form the intermediates gem-N₃P₃Cl₄(OSiPh₃)₂(ONa) and gem-N₃P₃Cl₄(ONa)₂, which yield gem-N₃P₃Cl₄(OSiPh₃)₂ when treated with Ph₃SiCl. The compounds N₃P₃Cl₅OSiPh₃ and N₃P₃(OSiPh₃)₀ are formed by the condensation reactions of N₃P₃Cl₅OBuⁿ and N₃P₃(OBuⁿ)₆, respectively, with Ph₃SiCl. The compound N₃P₃(OPh)₅OSiPh₃ is synthesized by the reaction between N₃P₃(OPh)₅Cl and Et₃SiONa to first give the intermediate N₃P₃(OPh)₅ONa, which yields N₃P₃(OPh)₅OSiPh₃ when reacted with Ph₃SiCl. The structural characterization and properties of these compounds are discussed. The crystal and molecular structure of gem-N₃P₃Cl₄(OSiPh₃)₂ has been investigated by single-crystal X-ray diffraction techniques. The crystals are monoclinic with the space group P2₁/c with a = 16.850(8), b = 12.829(4), c = 18.505(15) Å, and β = 101.00(6)° with V = 3927 ų and Z = 4. © 1996 John Wiley & Sons, Inc.     

Synthesen und Kristallstrukturen neuer heterobimetallischer Tantal‐Münzmetall‐Chalkogenido‐Cluster

Syntheses and Crystal Structures of Novel Heterobimetallic Tantalum Coin Metal Chalcogenido Clusters In the presence of phosphine the thiotantalats (Et₄N)₄[Ta₆S₁₇] · 3MeCN reacts with copper to give a number of new heterobimetallic tantalum copper chalcogenide clusters. These clusters show metal chalcogenide units some of which here already known from the chemistry of vanadium and niobium. New Ta—M‐chalcogenide clusters could also be synthesised by reaction of TaCl₅ and silylated chalcogen reagents with copper or silver salts in presence of phosphine. Such examples are: [Ta₂Cu₂S₄Cl₂(PMe₃)₆] · DMF ( 1 ), (Et₄N)[Ta₃Cu₅S₈Cl₅(PMe₃)₆] · 2MeCN ( 2 ), (Et₄N)[Ta₉Cu₁₀S₂₄Cl₈(PMe₃)₁₄] · 2MeCN ( 3 ), [Ta₄Cu₁₂Cl₈S₁₂(PMe₃)₁₂] ( 4 ), (Et₄N)[Ta₂Cu₆S₆Cl₅(PPh₃)₆] · 5MeCN ( 5 ), (Et₄N)[Ta₂Cu₆S₆Cl₅(PPh₂Me)₆] · 2MeCN ( 6 ), (Et₄N)[Ta₂Cu₆S₆Cl₅(P^tBu₂Cl)₆] · MeCN ( 7 ) [Ta₂Cu₂S₄Br₄(PPh₃)₂(MeCN)₂] · MeCN ( 8 ), [Cu(PMe₃)₄]₂[Ta₂Cu₆S₆(SCN)₆(PMe₃)₆] · 4MeCN ( 9 ), [TaCu₅S₄Cl₂(dppm)₄] · DMF ( 10 ), [Ta₂Cu₂Se₄(SCN)₂(PMe₃)₆] ( 11 ), [Cu(PMe₃)₄]₂[Ta₂Cu₆Se₆(SCN)₆(PMe₃)₆] · 4MeCN ( 12 ), [TaCu₄Se₄(PⁿPr₃)₆][TaCl₆] ( 13 ), [Ta₂Ag₂Se₄Cl₂(PMe₃)₆] · MeCN ( 14 ), _∞[TaAg₃Se₄(PMe₃)₃] ( 15 ). The structures of these compounds were obtained by X‐ray single crystal structure analysis.     

Zur Kenntnis der Dialkalimetalldichalkogenide β-Na2S2, K2S2, α-Rb2S2, β-Rb2S2, K2Se2, Rb2Se2, α-K2Te2, β-K2Te2 und Rb2Te2

On Dialkali Metal Dichalcogenides β-Na₂S₂, K₂S₂, α-Rb₂S₂, β-Rb₂S₂, K₂Se₂, Rb₂Se₂, α-K₂Te₂, β-K₂Te₂ and Rb₂Te₂ The first presentation of pure samples of α- and β-Rb₂S₂, α- and β-K₂Te₂, and Rb₂Te₂ is described. Using single crystals of K₂S₂ and K₂Se₂, received by ammonothermal synthesis, the structure of the Na₂O₂ type and by using single crystals of β-Na₂S₂ and β-K₂Te₂ the Li₂O₂ type structure will be refined. By combined investigations with temperature-dependent Guinier-, neutron diffraction-, thermal analysis, and Raman-spectroscopy the nature of the monotropic phase transition from the Na₂O₂ type to the Li₂O₂ type will be explained by means of the examples α-/β-Na₂S₂ and α-/β-K₂Te₂. A further case of dimorphic condition as well as the monotropic phase transition of α- and β-Rb₂S₂ is presented. The existing areas of the structure fields of the dialkali metal dichalcogenides are limited by the model of the polar covalence.     

La2O3 promotional effect to Co3O4/γ-Al2O3 catalyst in the oxidative dehydrogenation of ethylbenzene with CO2 as soft oxidant

Co₃O₄/γ-Al₂O₃ catalysts with variable Co₃O₄ loadings (5–20 wt%) and deposition of 15% Co₃O₄ on La₂O₃/γ-Al₂O₃ were prepared by wet impregnation method. La₂O₃-γ-Al₂O₃ support with variable composition of La₂O₃ (2–6 wt%) were prepared by co-precipitation method. All the catalysts were tested for oxidative dehydrogenation of ethylbenzene with CO₂ as soft oxidant. Among the Co₃O₄/γ-Al₂O₃ catalysts, 15% Co₃O₄/γ-Al₂O₃ has shown good performance and hence this catalyst has been chosen to investigate the effect of La₂O₃ species. CO₂ pulse chemisorption data indicate more amount of CO₂ uptake over 15% Co₃O₄/4%La₂O₃/γ-Al₂O₃ catalyst which clearly indicates that this catalyst exhibits good performance in ethylbenzene dehydrogenation with CO₂ as soft oxidant because of reverse water gas shift reaction. Temperature programmed reduction studies indicate that the Co₃O₄ catalysts follow two step reduction mechanism from Co₃O₄ to CoO and then to Co and La₂O₃ promotional effect is visible through facile reduction of Co₃O₄ species. La₂O₃ doping has a vital influence in getting enhanced ethylbenzene conversion, styrene yield and alleviates catalyst deactivation compared to that of unpromoted Co₃O₄/γ-Al₂O₃ catalyst. TGA studies indicate the presence low amount coke deposition during time-on-stream over 15% Co₃O₄/4%La₂O₃/γ-Al₂O₃ catalyst compared to 15% Co₃O₄/γ-Al₂O₃ catalyst.     

Synthesis and Ionic Conductivity of Lithium-conducting Titanium Phosphate Solid Electrolytes

Solid electrolytes were synthesized in the systems Li₂O-Al₂O₃-TiO₂-P₂O₅ and Li₂O-Al₂O₃-TiO₂-P₂O₅-H₂O-H₂O₂. Their ionic conductivities were studied and compared. The possibility of obtaining a film of Li_{1 . 3}Al_{0 . 3}Ti_{1 . 7}(PO₄)₃ solid electrolyte on a sapphire substrate from an aqueous peroxide solution of a precursor was analyzed.     

Phase diagrams of binary systems of alkylammonium tetrachlorometallates(II)

The phase diagrams of four binary systems (C₁₀H₂₁NH₃)₂CoCl₄?(C₁₆H₃₃NH₃)₂CoCl₄, (C₁₂H₂₅NH₃)₂CoCl₄?(C₁₆H₃₃NH₃)₂CoCl₄, (C₁₀H₂₁NH₃)₂ZnCl₄?(C₁₆H₃₃NH₃)₂ZnCl₄ and (C₁₂H₂₅NH₃)₂ZnCl₄?(C₁₆H₃₃NH₃)₂ZnCl₄ were investigated by means of DSC. These six compounds and their binary mixtures can retain energies between 74 and 115 J/g during solid-state transformations at temperatures between 70 and 105°C, and they are therefore being considered for potential use in solar energy systems.     

Synthesis and thermal decomposition of potassium trioxalatoaluminate hydrate

The preparation of pure K₃Al(C₂O₄)₃·mH₂O (2<m<3) is described. Dependent on the mode of preparation, the following were found to be contaminants of the desired product: K₂C₂O₄·1H₂O; KHC₂O₄; KHC₂O₄·H₂C₂O₄·2H₂O; H₂C₂O₄·2H₂O; different forms of aluminium oxide hydrate; K₄Al₂(OH)₂(C₂O₄)₄· (2+x)H₂O (0.7<x<1.7) and K₂Al₂(H₂O)₂(C₂O₄)₄· 4H₂O.     

Piperazine Functionalization of C70 for Incorporation into Supramolecular Assemblies

The photochemical reaction of piperazine with C₇₀ produces a mono‐adduct (N(CH₂CH₂)₂NC₇₀) in high yield (67 %) along with three bis‐adducts. These piperazine adducts can combine with various Lewis acids to form crystalline supramolecular aggregates suitable for X‐ray diffraction. The structure of the mono‐adduct was determined from examination of the adduct I₂N(CH₂CH₂)₂NI₂C₇₀ that was formed by reaction of N(CH₂CH₂)₂NC₇₀ with I₂. Crystals of polymeric {Rh₂(O₂CCF₃)₄N(CH₂CH₂)₂NC₇₀}_n?nC₆H₆ that formed from reaction of the mono‐adduct with Rh₂(O₂CCF₃)₄ contain a sinusoidal strand of alternating molecules of N(CH₂CH₂)₂NC₇₀ and Rh₂(O₂CCF₃)₄ connected through Rh?N bonds. Silver nitrate reacts with N(CH₂CH₂)₂NC₇₀ to form black crystals of {(Ag(NO₃))₄(N(CH₂CH₂)₂NC₇₀)₄}_n?7nCH₂Cl₂ that contain parallel, nearly linear chains of alternating (N(CH₂CH₂)₂NC₇₀ molecules and silver ions. Four of these {Ag(NO₃)N(CH₂CH₂)₂NC₇₀}_n chains adopt a structure that resembles a columnar micelle with the ionic silver nitrate portion in the center and the nearly non‐polar C₇₀ cages encircling that core. Of the three bis‐adducts, one was definitively identified through crystallization in the presence of I₂ as ¹²{N(CH₂CH₂)₂N}₂C₇₀ with addends on opposite poles of the C₇₀ cage and a structure with C_2v symmetry. In ¹²{I₂N(CH₂CH₂)₂N}₂C₇₀, individual ¹²{I₂N(CH₂CH₂)₂N}₂C₇₀ units are further connected by secondary I2???N2 interactions to form chains that occur in layers within the crystal. Halogen bond formation between a Lewis base such as a tertiary amine and I₂ is suggested as a method to produce ordered crystals with complex supramolecular structures from substances that are otherwise difficult to crystallize.     

Phase ratios in the K2O-V2O4-SO3 system at high sulfur trioxide concentrations

Phase ratios in the three-component oxide system K₂O-V₂O₄-SO₃ in the region of the sulfur trioxide concentrations corresponding to its concentrations in the active component of vanadium catalysts for SO₂ to SO₃ conversion have been studied using powder X-ray diffraction, IR spectroscopy, microscopy, and chemical analysis. Four individual compounds (K₂VO(SO₄)₂, K₂(VO)₂(SO₄)₃, K₂VO(SO₄)₂S₂O₇, and K₂(VO)₂(SO₄)₂S₂O₇) and K₂(VO)₂(SO₄)₂S₂O₇ and VOSO₄-base solid solutions of composition K₂(VO)_2+x (SO₄)_2+x S₂O₇ (0 ≤ x ≤ 1.5) were found in the system. K₂VO(SO₄)S₂O₇ and K₂(VO)₂(SO₄)₂S₂O₇ lose their sulfur trioxide when heated above 350°C under an inert atmosphere, and convert to K₂VO(SO₄)₂ and K₂(VO)₂(SO₄)₃, respectively. This implies that K₂VO(SO₄)₂S₂O₇ and K₂(VO)₂(SO₄)₂S₂O₇, as well as K₂(VO)_2+x (SO₄)_2+x S₂O₇ solid solution, cannot exist in the active component of real industrial catalysts.     

Reaktionen von Zinnchloriden mit Polysulfiden. Die Kristallstrukturen von (PPh4)2[SnCl2(S6)2], (PPh4)2[Sn4Cl4S5(S3)O] und (PPh4)2[SnCl6] · S8 · 2CH3CN

Reaction of Tin Chlorides with Polysulfides. Crystal Structures of (PPh₄)₂[SnCl₂(S₆)₂], (PPh₄)₂[Sn₄Cl₄S₅(S₃)O], and (PPh₄)₂[SnCl₆] · S₈ · 2CH₃CN . The reaction of PPh₄[SnCl₃] with Na₂S₄ in acetonitrile in the presence of small amounts of water yields (PPh₄)₂[Sn₄Cl₄S₅(S₃)O] and minor amounts of (PPh₄)₂[SnCl₂(S₆)₂], PPh₄Cl · 2S₈ and (PPh₄)₂[SnCl₆]. SnCl₄ is partially reduced by (PPh₄)₂S_x, PPh₄[SnCl₃] and (PPh₄)₂[SnCl₆] · S₈ · 2CH₃CN being produced. According to the X-ray crystal structure determination the [Sn₄Cl₄S₅(S₃)O]^2?-ion consists of an O atom that is coordinated by four Sn atoms which in turn are liked with one another by five single S atoms and one S₃ group. In the [SnCl₂(S₆)₂]^2?-ion the Sn atom is octahedrally coordinated by two Cl atoms in trans arrangement and by two chelating S₆ groups. Octahedral [SnCl₆]^2? ions and S₈ molecules in the crown conformation are present in (PPh₄)₄[SnCl₆] · S₈ · 2CH₃CN.     

Beiträge zum chemischen Transport oxidischer Metallverbindungen. V. Der Transport ternärer und quaternärer Mischferrite über ihre Metallchloride

Contributions to the Chemical Transport of Metal Oxides. V. Transport of Ternary and Quaternary Mixed Ferrites by their Chlorides The transport by means of HCl as transporting gas in a closed system in the case of the ternary mixed ferrites (Ni_0,8Fe_2,2O₄, Mn_0,75Fe_2,25O₄, Mn_1,286Fe_1,714O₄) and the quaternary mixed ferrites (Mg_0,5Mn_0,5Fe₂O₄, Mg_0,75Mn_0,536Fe_1,714O₄, Mg_0,281Mn_0,469Fe_2,25O₄, Mn_0,5Zn_0,5Fe₂O₄, Mn_0,5Zn_0,45Fe_2,05O₄, Ni_0,5Zn_0,5Fe₂O₄) between T₂ = 1100?1000°C and T₁ = 1000?800°C was investigated. Transported crystals were characterized by chemical analysis and the saturation magnetization, the transport rate has been checked. In the case of Mn_0,5Zn_0,45Fe_2,05O₄ two phases were transported. By discussing the phase diagram an explanation is given.