Die Reaktionen von Trithiazylchlorid mit Zirkoniumtetrachlorid Die Kristallstruktur von (S4N4CI)2[Zr2CI10]

Reactions of Zirconium Tetrachloride with Trithiazylchloride. Crystal Structure of (S₄N₄)[Zr₂Cl₁₀] Zirconium tetrachloride reacts with (NSCI)₃ yielding (S₃N₃CI₂)₂[Zr₂CI₁₀], S₄N₄[Zr₂CI₁₀], or (S₄N₄CI)₂[Zr₂CI₁₀], depending of the reaction conditions. These compounds were characterized by their i.r. spectra. They have an ionic structure containing the known ions S₃N₃CI₂⊕, S₄N₄^2⊕, S₄N₄CI^⊕, and the thus far unknown [Zr₂CI₁₀]^2? ion. According to the X-ray structure determination (2827 independent observed reflexions, R = 0.027), (S₄N₄CI)₂[Zr₂CI₁₀] crystallizes in the space group P&1macr; with the lattice constants a = 688, b = 1132, c = 1827 pm, α = 103.2°, β = 98.7° and γ = 91.9⁰ and with Z = 2 formula units per unit cell. The structure is built up from S₄N₄CI^⊕ ions, which are nearly identical as in S₄N₄CI[FeCI₄] and from [Zr₂CI₁₀]^2? ions in which two chloro bridges join two edge-sharing octahedra.     

Die Reaktion von Trithiazylchlorid mit Titantetrachlorid Die Kristallstruktur von (S4N5)2[Ti2Cl10]

Reaction of Trithiazyl Chloride with Titanium Tetrachloride. Crystal Structure of (S₄N₅)₂[Ti₂Cl₁₀] In the reaction of trithiazyl chloride with titanium tetrachloride, chlorine is abstracted and the brown-yellow adduct TiCl₄(N₂S₂) is obtained. In this compound — according to its i.r. spectrum — a N₂S₂ ring is bonded to the titanium via the N atoms, thus forming a polymer. As a by-product, brown crystalline (S₄N₅)₂[Ti₂Cl₁₀] forms. Its crystal structure was determined and refined with X-ray diffraction data (R = 0.042 for 812 reflexions). It crystallizes in the monoclinic space group P2₁/c with two formula units per unit cell. The lattice constants are a = 670, b = 1 633, c = 1108 pm, β = 97.24°. The structure consists of S₄N₅^⊕ cations, which are nearly equal to those in [S₄N₅]Cl, and [Ti₂Cl₁₀]^2? anions, which are nearly identical with those in (PCl₄)₂[Ti₂Cl₁₀].     

Reaktionen von Oxiden der Elemente der V. Hauptgruppe mit Trithiazylchlorid Kristallstruktur von (S5N5)4[As8Cl28] · 2 S4N4

Reactions of Element Oxides of the Fifth Main Group with Trithiazyl Chloride. Crystal Structure of (S₅N₅)₄[As₈Cl₂₈] · 2 S₄N₄ Whereas P₄O₁₀ does not react with (NSCl)₃, the oxides As₂O₃, Sb₂O₃, and Bi₂O₃ react under formation of (S₅N₅)₄[As₈Cl₂₈] · 2 S₄N₄, S₅N₅[SbCl₆] and a mixture of S₄N₅[BiCl₄] and S₄N₄Cl[BiCl₄], respectively. The products were characterized by their IR spectra. The crystal structure of (S₅N₅)₄[As₈Cl₂₈] · 2 S₄N₄ was determined by means of X-ray diffraction (1168 independent observed reflexions, R = 0.059). Crystal data: tetragonal, space group P4 2₁c, Z = 2, a = 1596.6, c = 1520.1 pm. The compound consists of planar S₅N₅^⊕ cations, octameric anions [As₈Cl₂₈]^4? and S₄N₄ molecules. The S₅N₅^⊕ ions and the S₄N₄ molecules show positional disorder, which very probably is of dynamical type for the S₅N₅^⊕ ion. The [As₈Cl₂₈]^4? ions can be described as a (so far unknown) [As₄Cl₁₆]^4? ion with cubane-like structure (As? Cl bridging distances between 286 and 305 pm) to which four AsCl₃ molecules are attached via chloro bridges with As? Cl bond lengths between 314 and 328 pm.     

Zur Chemie der Chlorthionitrenkomplexe des Rheniums Die Kristallstruktur von [N(SCl)2]⊕ [Re2Cl9]⊖

Chemistry of Chlorothionitrene Complexes of Rhenium. Crystal Structure of [N(SCl)₂]⊕ [Re₂Cl₉]? By reaction of S₃N₂Cl₂ with ReCl₅ the chlorothionitrene complex [ReCl₃(NSCl)₂]₂ is obtained in good yield; it has a dimer structure with chloro bridges. By the same reaction in POCl₃ solution the solvate [ReCl₃(NSCl)₂OPCl₃] is obtained. Instead, when a molar ratio of ReCl₅ and S₃N₂Cl₂ of 2:1 is taken, the product is [N(SCl)₂][Re₂Cl₉]. [ReCl₄(NSCl)OPCl₃] and excess PPh₃ react to give the nitrido complex [ReNCl₂(PPh₃)₂]. The crystal structure of [N(SCl)₂][Re₂Cl₉] was determined and refined with X-ray diffraction data (1021 independent reflexions, R = 0.031). It crystalizes in the space group C2/c with four formula units per unit cell (a = 1197, b = 1288, c = 1144 pm, ß = 107.83°). The [N(SCl)₂]⊕ cations have exactly C₂ and approximately C_2v symmetry; the NS bond lengths of 162 pm and the bond angles SNS (133.6°) and NSCl (117.6°) deviate considerably from the values of known [N(SCl)₂]⊕ structures. The [Re₂Cl₉]? anion consists of two face sharing octahedra and has a Re—Re distance of 270 pm. I. r. spectra of all compounds are reported and discussed.     

Die Kristallstruktur von (Ph4P)2[Be4Cl4(μ‐N3)6]

Suitable single crystals for X‐ray analysis of the recently published azido beryllate (Ph₄P)₂[Be₄Cl₄(μ‐N₃)₆] ( 1 ) [1] were obtained by a modified synthetic route, and the crystal structure of 1 was determined. The compound crystallizes isotypically with the corresponding bromo derivative [1] in the space group C2/c with 12 formula units per unit cell. Lattice dimensions at 193 K: a = 4125.5(1), b = 2001.7(1), c = 2050.4(1) pm, β = 101.05 (1)°, R₁ = 0.0359. The structure contains adamantanlike dianions [Be₄Cl₄(μ‐N₃)₆]^2? with a Be₄N₆ core forming by the bridging function of the α‐nitrogen atoms of the azido groups.     

Zur Bestimmung von Schwefelwasserstoff mit N,N-Dimethyl-p-phenylendiamin und Eisen(III)-chlorid

Zusammenfassung Die Reaktion von Schwefelwasserstoff mit N,N-Dimethyl-p-phenylendiamin und Eisen(III)-chlorid in salzsaurer Lösung wurde näher unterucht. Das Spektrum der Reaktionslösung weist neben dem für Methylenblau typischen Absorptionsmaximum bei 670 nm ein weiteres bei 740 nm auf, das jedoch nicht auf der Bildung eines weiteren Farbstoffs beruht, sondern sehr wahrscheinlich durch eine Wechselwirkung von Methylenblau mit einem Chloroferrat(III)-komplex hervorgerufen wird. Die Farbstoffbildung und das Auftreten der Extinktion bei 740 nm sind in starkem Maße von der Salzsäurekonzentration des Reaktionsgemisches abhängig. Optimale Bedingungen für die Farbstoffbildung und -messung erreicht man bei Anwendung eines in bezug auf die Stöchiometrie der Reaktion nicht zu großen Überschusses an Eisen(III)-chlorid (etwa fünffach) und einer HCl-Konzentration von rund 1–3%. Unter den angewendeten Bedingungen wird das Reaktionsgleichgewicht bereits nach 10 min erreicht. Die Farblösungen sind lange Zeit stabil.

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Summary The reaction of hydrogen sulphide with N,N-dimethyl-p-phenylenediamine and iron(III)-chloride in diluted hydrochloric acid was investigated. In this system, additionally to the absorption maximum of pure methylene blue (670 nm), a second absorption maximum at 740 nm was observed. This maximum is not caused by the formation of a second dye but probably by the interaction between methylene blue and a chloroferrate(III) complex. The formation of the dye and the absorption at 740 nm are strongly dependent on the concentration of hydrochloric acid in the mixture. Optimum conditions for the formation of the dye and its measurement are realized by a moderate (about five times) excess of FeCl₃ and by a concentration of hydrochloric acid of 1–3%. Under these conditions the equilibrium of the reaction is reached already after 10 min. The solution of the dye formed is stable.

     

[PPh3Cl]⊕[ReCl4(N2S2)]⊖ Synthese,IR-Spektrum und Kristallstruktur

[PPh₃Cl]^⊕[ReCl₄(N₂S₂)]^?; Synthese, IR-Spektrum und Kristall Strukture The title compound is prepared by the reaction of [ReCl₃(NSCl)₂(POCl₃)] with triphenylphosphane; it formes black crystals. The crystal structure determination was solved with X-ray methods (2861 observed independent reflexions, R = 0.038). The compound crystallizes monoclinic in the space group P2₁/n with four formula units per unit cell. The structure consists of [PPh₃Cl]^⊕ cations and [ReCl₄(N₂S₂)]^? anions, in which the rhenium atom is surrounded octahedrally by four chlorine ligands and the N atoms of a ReN₂S₂-five-membered ring in cis-position (symmetry C_2v). The Re? N bond lengths (181 pm) and the NS bond lengths (152 pm) are in the range of double bonds; the S? S distance is very long (253 pm). The i.r. spectrum is reported.     

Die Extraktion von Eisen(III)-chlorid aus salzsauren L?sungen mit Tributylphosphat

Ohne Zusammenfassung     

Die Reaktionen von Dimethylsulfoxid mit Molybdäntetrabromid und Molybdändibromid-dinitrosyl Die Kristallstruktur von [MoBr2(NO)2(OSMe2)2]

Reactions of Dimethyl Sulfoxide with Molybdenum Tetrabromide and Molybdenum Dibromide Dinitrosyl. Crystal Structure of [MoBr₂(NO)₂(OSMe₂)₂] In the cold molybdenum tetrabromide reacts with an equivalent amount of dimethyl sulfoxide forming the solvate [MoBr₄(OSMe₂)₂]; excess dimethyl sulfoxide yields [MoO₂Br₂(OSMe₂)₂] which is also obtained by other methods. Molybdenum dibromidedinitrosyl forms the solvate [MoBr₂(NO)₂(OSMe₂)₂] in the reaction with dimethyl sulfoxide. According to the i.r. spectra all complexes display O-coordination of the OSMe₂ molecules. [MoBr₂(NO)₂(OSMe₂)₂] crystallizes monoclinic in the space group P2₁/c with four formula units per unit cell. The cell dimensions are a = 1236, b = 892, c = 1305 pm, β = 95.2°. 1662 independent observed reflexions were used for refinement; R = 3.8%. The molybdenum atoms are six-coordinated, the O atoms of the dimethyl sulfoxide molecules are in trans-position to the nitrosyl ligands, which form linear groups Mo? N? O.     

S4N3⊕[ReCl4(NSCl)2]⊖ Synthese und Kristallstruktur

S₄N₃^⊕[ReCl₄(NSCl)₂]^?. Synthesis and Crystal Structure S₄N₃^⊕[ReCl₄(NSCl)₂]^? is formed as a byproduct in the reaction of Re₂(CO)₁₀ with excess trithiazyl chloride. The compound is characterized by a crystal structure analysis by X-ray methods. S₄N₃[ReCl₄(NSCl)₂] crystallizes in the noncentrosymmetric space group P2₁2₁2₁ with four formula units per unit cell and the lattice dimensions a = 980, b = 1205, c = 1362 pm (2376 observed, independent reflexions; R = 0.076). The compound consists of the well known cyclic planar S₄N₃^⊕-cations and anions [ReCl₄(NSCl)₂]^?, in which the rhenium atom is coordinated octahedral by four Cl atoms and two cis-positioned NSCl ligands. The mean Re? N and N? S bond lengths (177 pm and 158 pm) correspond to double bonds. The bond lengths and angles are much like in the structure of AsPh₄[ReCl₄(NSCl)₂]; however the chlorine atoms of the NSCl ligands are turned to each other.     

Zur volumetrische Titanbestimmung mit Eisen(III)-chlorid

Ohne Zusammenfassung     

Komplexierung von Gold mit N,N-Dialkyl-N′-benzoylthioharnstoffen: Die Kristallstruktur von N,N-Diethyl-N′-benzoylthioureatogold(I)-chlorid

Complex Formation of Gold with N,N-Dialkyl-N′-benzoylthioureas: The Crystal Structure of N,N-0Diethyl-N′-benzoylthioureatogold(I) Chloride N,N-Diethyl-N′-benzoylthioureatogold(I) chloride AuCiS₁₂H₁₆N₂O crystallizes in the monoclinic space group P2₁/c. The cell parameters are a = 18.407(4), b = 5.456(1) and c = 196.322(3) Å, β = 113.6/8(1)°. The structure was solved with direct techniques and refined to final R-value of 5.92%. Gold(I) forms a monodentately sulfur-coordinated complex with the ligand N,N-Diethyl-N′-benzoylthiourea. The coordination sphere around Au(I) shows a nearly linear arrangement of sulfur and chloride.     

Thionitrosylkomplexe des Osmiums. Die Kristallstruktur von AsPh4[OsCl4(NS)2Cl]

Thionitrosyl Complexes of Osmium. Crystal Structure of AsPh₄[OsCl₄(NS)₂Cl] The reaction of osmium pentachloride with trithiazyl chloride (NSCl)₃ yields the thiazylchloride complex [OsCl₄(NSCl)₂], from which the thionitrosyl complex AsPh₄[OsCl₄(NS)₂Cl] is obtained by reaction with AsPh₄Cl in CH₂Cl₂. From this, the neutral thionitrosyl complex [OsCl₄(NS)₂] forms by chloride abstraction with gallium trichloride. The crystal structure of AsPh₄[OsCl₄(NS)₂Cl] was determined and refined with the aid of X-ray diffraction data (R = 0.033, 2161 reflexions). It crystallizes in the monoclinic space group P2₁/c with four formula units per unit cell. The lattice constants are a = 1735, b = 1058, c = 1578 pm and β 95.64°. In the [OsCl₄(NS)₂Cl]^? ion the osmium is octahedrally coordinated by four Cl atoms and two NS groups in a cis arrangement. The NS groups are essentially linear with the bond lengths Os?N 184 pm and N?S 146 pm. Loosely attached to one of the S atoms there is a Cl atom (S? Cl distance 228 pm); in the crystal it statistically belongs to both S atoms with an occupation probability of one half, and it cannot be decided whether there is a dynamical fluctuation between the S atoms or a static positional disorder. However, according to the i.r. spectrum the dynamical model seems more probable.     

Aluminiumalkyle mit Heteroatomen. III. Über Reaktionen von Titan(IV)-chlorid mit Tris(trimethylsilylalkyl)-aluminium-Verbindungen

Aluminium Alkyls with Heteroatoms. III. On Reactions of Titanium(IV) Chloride with Trimethylsilylmethyl Aluminium Compounds Trimethylsilylmethyl titanium trichloride can be obtained by reaction of titanium(IV) chloride with tris(trimethylsilylmethyl)aluminium diethyl ether (1:1). Its catalytic activity for polymerisation of butadiene has been investigated.     

Die Kristallstruktur von [Cl4P{i-Prop-NC(Cl)N-i-Prop}]

Crystal Structure of [Cl₄P{i-Prop-NC(Cl)N-i-Prop}] The monomeric di-isopropylcarbodiimide complex [Cl₄P{i-Prop-NC(Cl)N-i-Prop}] crystallizes in the monoclinic space group C2 with 4 formula units in the unit cell and with the lattice constants a = 1391.2(2), b = 708.6(1), c = 1463.5(2) pm and β = 95.76(1)°. The structure was refined to an R-value of 0.026 (2084 independent, observed reflexions). Main parts of the IR and Raman spectrum of the compound are discussed.     

Die Kristallstruktur von [Cl3PNPCl3][VOCl4]

Investigations on Electronically Conducting Oxide Systems. XIV. Solid Solutions and Conductivity in the System MgTiO₃? Ti₂O₃ Solid solution formation and conductivity is reported for the system Mg_1?xTiTiO₃ (0 < x < 1). Ti^III atoms are predominantly substituted in pairs for Mg^II and Ti^IV. In the range of low x values Ti^III? Ti^III bonds typical for Ti₂O₃ in the semiconducting state are very weakened because of the distances preserved in the host lattice of MgTiO₃. Up to x = 0,5 EPR measurements at 77 K indicate magnetic “dimers” with S = 1 at a distance of 550 pm resulting from antiparallel spin orientation of the Ti^III pairs and transfer of the magnetic interaction by super exchange to a next-neighboured Ti^III pair. Electrical conductivity is caused by polaron hopping. The steep increase in the range of small Ti^III concentration is interpreted by a screening field approximation.     

Die Bromokomplexe von Molybdän(IV) [MoBr6]2⊖ und [Mo2Br10]2⊖. Die Kristallstruktur von (PPh3Me)2[MoBr6] · 2 CH2Br2

Bromo Complexes of Molybdenum(IV) [MoBr₆]^2? and [Mo₂Br₁₀]^2?. Crystal Structure of (PPh₃Me)₂[MoBr₆] · 2 CH₂Br₂ The bromomolybdates(IV) (PPh₃Me)₂[MoBr₆] · 2 CH₂Br₂ and (PPh₄)₂[Mo₂Br₁₀] are obtained by reactions of molybdenum tetrabromide with PPh₃MeBr and PPh₄Br, respectively. They form black-brown, hydrolysis sensitive crystal powders. The crystal structure of (PPh₃Me)₂[MoBr₆] · 2 CH₂Br₂ was determined by X-ray diffraction (2376 independent observed reflexions, R = 0.082). Crystal data: a = 1024, b = 1131, c = 1179 pm, α = 108.2°, β = 106.8°, γ = 99.0°, space group P1 , Z = 1. The compound consists of PPh₃Me⁺ ions, CH₂Br₂ molecules and nearly octahedral [MoBr₆]^2? ions with MoBr bond lengths between 252.7 and 254.0 pm.     

Bestimmung von zwei- und dreiwertigem Titan in Chloridschmelzen mit Eisen (III)-chlorid

Ohne Zusammenfassung     

Die titrimetrische Bestimmung von Eisen (III) mit Natriumthiosulfat

Ohne Zusammenfassung