Über anomale Mischkristalle vom Typ Ammoniumchlorid-Kobalt(II)chlorid-Wasser

Zusammenfassung Untersucht wurde das System NH₄Cl–CoCl₂–H₂O bei 25,0°C mit und ohne Überschuß an HCl in der Lösung. Bestimmt wurden die Kristallisationsbereiche der anomalen Mischkristalle auf der Basis von Ammoniumchlorid, der anomalen Mischkristalle auf der Basis des Doppelsalzes 2 NH₄Cl·CoCl₂·2H₂O und der Kristallisationsbereich von CoCl₂·6H₂O. Die Gegenwart eines Säureüberschusses in der Lösung übt eine entsalzende Wirkung aus.Es wird gezeigt, daß die anomalen Mischkristalle Systeme darstellen, in denen mit der Zeit langsame Veränderungen eintreten. Die Einbaukomponente im Ammoniumchlorid ist das Doppelsalz 2 NH₄Cl·CoCl₂·2 H₂O. Dieses liegt metastabil im Kristallisationsbereich des Ammoniumchlorids vor und zerfällt langsam in seine Bestandteile. Das dabei gebildete Kobalt(II)chlorid verbleibt adsorbiert im Kristallverband des Ammoniumchlorids und wird zusätzlich hydratisiert.

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Anomalous mixed crystals of the ammonium chloride-cobalt(II) chloride-water type

The system NH₄Cl–CoCl₂–H₂O is investigated at 25.0°C, with and without excess of HCl. The crystallization ranges of the anomalous mixed-crystals on the basis of ammonium chloride, of the anomalous mixed-crystals on the basis of the double-salt 2NH₄Cl·CoCl₂·2H₂O and of CoCl₂·6H₂O were determined. The presence of HCl in the solution decreases the solubilities of the different phases occurring in the above system.It is shown that the anomalous mixed-crystals represent systems undergoing slow changes in time. The component which is built in ammonium chloride is the double-salt 2 NH₄Cl·CoCl₂·2 H₂O. It is unstable in the crystallization range of ammonium chloride. This is why it decomposes slowly, into its components. The cobalt(II) chloride set free remains adsorbed in the ammonium chloride crystals and is hydrated additionally.

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Mit 4 Abbildungen

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Am Versuchsteil hatte auch FrauMargarita Sheleva-Vogel Anteil, wofür ihr die Autoren ihren Dank aussprechen.     

Die Kristallstruktur des Thallium(I)-hexaiodomercurat(II), Tl4Hgl6

Crystal Structure of Thallium(I) Hexaiodomercurate(II), Tl₄HgI₆ In the structure of the tetragonal Tl₄HgI₆ (a = 944.6 pm, c = 926.0 pm, Z = 2, space group P 4/mnc) isolated, in c-direction compressed HgI₆ octahedra are situated. The mercury atoms are disordered; they occupy statistically 4 positions in the equatorial plane of the octahedra in such a manner that strongly deformed HgI₄ tetrahedra are produced. The thallium atoms are eightfold coordinated like a bicapped trigonal prism. The relationship between the Tl₄HgI₆ structure and the cubical K₂PtCl₆ type will be discussed.     

Thallium(I)

Ohne Zusammenfassung     

Thallium(I)

Ohne Zusammenfassung     

Die FIR-Spektren gemischter Hexahalogeno-Osmate (IV) vom OsCl6-nXn-Typ (X = Br,I) und ihre Normalkoordinatenanalyse

The far infrared (FIR) spectra of [OsCl₅I]²⁻, cis-[OsCl₄I₂]²⁻, fac-[OsCl₃I₃]²⁻, [OsCl₅Br]²⁻ and cis-[OsCl₄Br₂]²⁻ (Cs-salts) have been recorded at temperatures down to 35 K. The measured band peaks are assigned to symmetry levels using group theory arguments and normal coordinate analyses starting from corresponding octahedral OsX²⁻₆ compounds. In general, OsX bonding properties can be transferred from one compound to another except for XOsY axes where distinct trans-effects are operative. Normal coordinates are also able to explain weak oscillator strengths when predicting small changes of transition dipole moments.     

Untersuchungen zur Struktur von Thallium(I)-halogenomercuraten(II)

Investigations on the Structure of Thallium(I) Halide Mercurates(II) Tl₄HgBr₆ crystallizes tetragonal with a = 8.978, c = 8.812 Å and Z = 2 in the space group P4/mnc. Singlecrystal methods revealed isolated HgBr₆-octahedra, compressed alonged the [001] axis, with thallium atoms between them. The results have been extended to clarify the structures of the isomorphous compounds (NH₄)₄HgBr₆ (a = 9.011, c = 8.660 Å), Tl₄HgJ₆ (a = 9.529, c = 9.387 Å) and Tl₄HgCl₂Br₄ (a = 8.896, c = 8.735 Å). It was impossible to obtain Tl₄HgCl₆; all attempts resulted in the formation of Tl₁₀Hg₃Cl₁₆, which crystallizes tetragonal (a = 8.477, c = 23.699 Å).     

Einkernige und zweikernige Kupfer(I)‐Komplexe vom Typ LCuCl,LCu2Cl2 und LCu2ClX [L = P(C6H4CH2NMe2)3; X = Br,I]

The title compounds 3‐5 are accessible by treatment of P(C₆H₄CH₂NMe2)₃( 1 ) with CuX ( 2a : X = Cl, 2b : X = Br, 2c : X = I) in the ratio of 1:1 or 1:2 in very good yields. Reaction of 1 with equimolar amounts of 2a affords the copper(I) chloride [P(C₆H₄CH₂NMe2)₃]CuCl ( 3 ). With a further equivalent of 2a homobimetallic [P(C₆H₄CH₂NMe2)₃]Cu₂Cl₂ ( 4 ) is formed, which also can be synthesized by the reaction of 1 with two equivalents of 2a. Complex 3 reacts with CuX (X = Br, I)to afford [P(C₆H₄CH₂NMe2)₃]Cu₂ClX ( 5a : X = Br; 5b : X = I) in which mixed halides are present. The newly synthesized complexes 3‐5 were characterized by elemental analyses, by their IR‐, ¹H‐, ¹³C{¹H}‐ and ³¹P{¹H}‐NMR spectra as well as by mass spectrometrical studies. The solid‐state structures of complexes 3 and 4 are reported. Mononuclear 3 crystallizes in the monoclinic space group P2₁/c with the cell parameters a = 14.285(2), b = 10.853(2), c = 17.425(2) Å , β = 103.310(10)?, V = 2628.9(7) Å ³ and Z = 4 with 4053 observed unique reflections; R₁ = 0.0314. The crystal structure of 3 consists of monomeric molecules with planar coordinated copper(I) centres (CuClNP). Homobimetallic 4 crystallizes in the monoclinic space group P2₁/n with a = 23.905(4), b = 10.874(3), c = 25.314(5), β = 99.130(10)?, V = 6497(2) /Aring; ³ and Z = 4 with 9021 observed unique reflections; R₁ = 0.0480. In 4 one of two copper(I) centres possesses a distorted trigonal‐pyramidal environment, while the other one is almost square‐pyramidal coordinated. The Cu₂Cl₂ segment resembles to a building block which is set up by a contact ion pair consisting of Cu⁺ and [CuCl₂]^‐ , respectively.     

Thallium(I)-Uranates(VI)

The solid state preparation, thermal and hydrolytic characteristics of thallium(I)—uranates(VI) are described. The phases identified were Tl₂UO₄, Tl₂U₂O₇ and a range of solid solution (Tl₂O. 2,33 UO₃? Tl₂O. 6 UO₃). The thallium uranates are isostructural with the corresponding potassium uranates. Tl₂U₂O₇ is the stable phase formed from the other uranates on hydrolytic treatment. The thallium uranates lose thallium(I) oxide on heating to temperatures above 750°C and the order of thermal stability is Tl₂U₆O₁₉～Tl₂U₃O₁₀～Tl₂U₂O₇»Tl₂UO₄.     

Platinum(II) and platinum(IV) complexes of 2-amino-4, 6-dimethylpyrimidine

Summary Platinum(II) and platinum(IV) complexes of 2-amino-4, 6-dimethylpyrimidine, ADMPY, have been prepared. Solids of formula Pt(ADMPYH⁺)Cl₃, Pt(ADMPY)₂Cl₄ and Pt(ADMPY)₂Cl₄·2HCl have been isolated and characterized by elemental analyses in conjuction with i.r. and n.m.r. spectra. A paramagnetic tan to reddishbrown complex has been reproducibly prepared from the direct reaction of K₂PtCl₄ and ADMPY at pH 6.     

Blei und Thallium(I)

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Kalium, Rubidium, Caesium und Thallium(I)

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Neue schnelle Ionenleiter vom Typ MMIIICl6 (MI = Li,Na, Ag; MIII = In,Y)

Novel Fast Ion Conductors of the Type M M^IIICl₆ (M^I = Li, Na, Ag; M^III = In, Y) The ternary chlorides Li₃InCl₆, Na₃InCl₆, Ag₃InCl₆, and Li₃YCl₆ have been studied by difference scanning calorimetry, high-temperature X-ray, infrared, and high-temperature Raman methods. Impedance spectroscopic measurements exhibit fast ionic conductivity increasing in the sequence Na₃InCl₆ < Li₃YCl₆ < Ag₃InCl₆ < Li₃InCl₆. In the range of 300°C, Li₃InCl₆ is the best lithium ion conductor known so far (σ = 0,2 Ω^?1 cm^?1 at 300°C). With the exception of Na₃InCl₆, the chlorides exhibit complicated order-disorder phase transitions.     

Thallium(II) in the chemically induced thallium(I)-Thallium(III) exchange

The rate of the electron exchange between thallium(I) and thallium(III) induced by iron(II) has been measured at various concentrations of Tl(I), Tl(III), and Fe(II).²⁰⁴Tl tracer, initially in the Tl(I) state, was used. Exchange induced by the separation method was less than 0.01%. The mechanism earlier discussed is $$\begin{gathered} Tl^{III} + Fe^{II} \rightleftharpoons Tl^{II} + Fe^{III} \left( {k_1 ,k_{ - 1} } \right) \hfill \\ Tl^{II} + Fe^{II} \rightharpoonup Tl^I + Fe^{III} \left( {k_2 } \right) \hfill \\ *Tl^I + Tl^{II} \rightleftharpoons *Tl^{II} + Tl^I \left( {k_I } \right) \hfill \\ *Tl^{II} + Tl^{III} \rightleftharpoons *Tl^{III} + Tl^{II} \left( {k_{III} } \right), \hfill \\ \end{gathered} $$ which provides an exchange path in addition to the two-electron reaction^*Tl^I+Tl^III?^*Tl^III+Tl^I (k_ex). The rate law deduced from this mechanism agrees with experiment over a limited range of conditions but fails to account for the observed effect at low concentrations of Tl(I). The additional rate can be represented by inclusion of a term in which the rate of the induced exchange is independent of the concentration of Tl(I). When treated according to the resulting complete rate law the data are consistent with earlier photochemical studies. The present results in combination with other data give k₂=3·10⁶ M^?1·sec^?1 in 1M perchloric acid at 25°C. This is in satisfactory agreement with a recent pulse radiolysis measurement as well as with independent flash photolysis studies.     

Thallium(I) -bis(trimethylsilyl) amid

The reaction of LiN(SiMe₃)₂ With TlCl in toluene yields the bis(trimethylsilyl)amino derivative of thallium(I) (1). In the gaseous phase and in benzene solution the compound is mainly monomeric, whereas in the solid state the amide 1 consists of cyclic dimers, which are linked to infinite chains by intermolecular Tl Tl contacts.     

Die Extraktion von Thallium(I)

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Thallium(I), Silver(I), and Mixed Thallium(I)/Copper(I) Clusters with Bridging {Me2Si(N‐C6H4‐2‐SPh)2}2– Ligands

The S‐functionalized aminosilane Me₂Si(NH‐C₆H₄‐2‐SPh)₂ (H₂L) ( 1 ) was prepared from dichlorodimethylsilane and lithiated 2‐(phenylthio)aniline. Treatment of compound 1 with two equivalents of n‐butyllithium led to the dilithium derivative Li₂L, which was used in subsequent reactions with MCl (M = Tl, Cu, Ag) to prepare the complexes [Tl₂L] ( 2 ), [Cu₂Tl₂L₂] · 2THF ( 3a ), [Cu₂Tl₂L₂(THF)₂] ( 3b ), and [Ag₄L₂(THT)₂] ( 4 ) (THT = tetrahydrothiophene). Compound 2 consists of two thallium atoms, which are connected by a L^2– ligand to give a puckered Tl₂N₂ ring with Tl–N distances of 255(1)–268(1) pm. Compounds 3a and 3b are heterobimetallic complexes, which are based on [Cu₂L₂]^2– cores featuring a Cu₂N₄Si₂ ring with linearly coordinated copper atoms [Cu–N: 190.7(3)–192.5(3) pm] and two peripherally attached Tl atoms [Tl–N: 272.7(3)–281.9(3) pm]. The molecular structure of the tetranuclear silver(I) complex 4 is closely related to the structure of compounds 3a and 3b by replacement of the Cu and Tl atoms with Ag atoms. The Ag–N distances are 217.5(3)–245.7(3) pm.