Die Reaktion von TiCl4 und ZrCl4 mit (SeCN)2

Reaction of TiCl₄ and ZrCl₄ with (SeCN)₂ By reaction of TiCl₄ and ZrCl₄ with (SeCN)₂ in CS₂ the compounds TiCl₃NCSe and ZrCl₃NCSe were obtained. According to their vibrational spectra, the selenocyanate groups form bridges between the metal atoms via their N and Se atoms.     

Die Reaktion von Molybdänpentachlorid mit Trichlornitromethan; die Kristallstruktur von [MoOCl3 · POCl3]2

Reaction of Molybdenum Pentachloride with Trichloronitromethane. Crystal Structure of [MoOCl₃ · POCl₃]₂ An improved method for the preparation of MoO₂Cl₂ by the reaction of MoCl₅ with CCl₃NO₂ is reported. In the presence of the solvens POCl₃, molybdenum pentachloride reacts with trichloronitromethane forming the oxonitrosyl complex Mo(NO)OCl₃ · POCl₃. In CH₂Cl₂ solution this complex is decomposed forming [MoOCl₃ · POCl₃]₂. The crystal structure was solved by X-ray methods. [MoOCl₃ · POCl₃]₂ crystallizes monoclinic in the space group P2₁/c with two dimers in the unit cell (R = 0.07, 2327 independent reflexions). The complex dimerizes by symmetric chloro bridges; the oxoligand is in terminal position. The MoO bond length of 163 pm corresponds with a Mo?O triple bond. The POCl₃ molecule is coordinated in position trans to the oxoligand. The IR spectra are reported and assigned.     

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.     

Über die Reaktionen von N-Chloracetonimin mit Molybdänpentachlorid und Wolframhexachlorid Die Kristallstruktur von Me2CNH2[MoOCl4]

Reactions of N-Chloroacetoneimine with Molybdenum Pentachloride and Tungsten Hexachloride. Crystal Structure of Me₂C?NH₂[MoOCl₄] WCl₆ reacts with N-chloroacetoneimine under elimination of chlorine and formation of pentachloro-isopropylideneimino-tungsten(VI), Cl₅W?N?CMe₂, a brown-black crystal powder, which was characterized by i.r. spectroscopy. MoCl₅ reacts in a similar way, although only a product mixture can be obtained. Partial hydrolysis of this mixture yields isopropylideneiminium-tetrachlorooxomolybdate(V), Me₂C?NH₂⁺[MoOCl₄]^?, of which the crystal structure was determined (2323 unique observed reflexions, R = 0.049). Space group P2₁/c, Z = 4, a = 878.6, b = 907.2, c = 1252.2 pm, β = 91.29°. The compound consists of Me₂C?NH₂⁺ ions with a planar arrangement of the skeletal atoms and a CN bond length of 126.7 pm and of dimeric, centrosymmetric anions [MoOCl₄]₂^2? having Mo atoms linked via asymmetric chloro bridges (MoCl distances 238.4 and 307.6 pm). The longer Mo? Cl contacts are located in the trans-positions of the terminal oxoligands (MoO distance 164 pm).     

Das Reaktionsverhalten von Phosphorpentahalogeniden mit Übergangsmetallcarbonylen. III. Die Reaktion von PBr5 mit den Hexacarbonylen des Molybdäns und Wolframs

Reactivity of Phosphorus Pentahalides with Transition Metal Carbonyls. III. Reactivity of PBr₅ with Hexacarbonyls of Molybdenum and Tungsten PBr₅ reacts with M(CO)₆ (M = Mo, W) already at room temperature in CH₃CN as solvent. Independend on the reaction condition WBr₄(CH₃CN)₂ was obtained in the reaction of PBr₅ with W(CO)₆. In the case of Mo(CO)₆ the complexes MoBr₃(CH₃CN)₃ and MoBr₄(CH₃CN)₂, respectively, were isolated depending on the amount of PBr₅ and the reaction temperature. The structure of the products is discussed on the basis of the IR spectra and of magnetic moments.     

Die Reaktion von wässerigem Epichlorhydrin mit Hydroxid- und Phenolat-Ionen

The reactions of epichlorhydrin with hydroxide and phenolate ions in water are shown to proceed by the same mechanism as the reactions of other epoxides with nucleophilic reagents, and not by direct attack on the halogen-substituted carbon. The effect of solvent composition on the linear free energy correlations, like the equation of SWAIN & SCOTT , is discussed on the basis of recent literature data.     

Die Reaktion von UV- und UVI-Verbindungen mit SOCl2

Reaction of U^V and U^VI Compounds with SOCl₂ UO₃, UO₂Cl₂, UCl₆, and UCl₅ reacted with OSCl₂ yield always UCl₅ · SCl₂, [SCl₃]⁺ [UCl₆]^? or a mixture of these compounds, but not an adduct UCl₅ · OSCl₂. An X-ray study was carried out with single crystals of [SCl₃]⁺[UCl₆]^?. It crystallizes in the orthorhombic space group P2₁2₁2₁ with the lattice constants a = 1066.8, b = 1071.2, c = 1133.3 pm and with Z = 4, containing isolated pyramidal SCl₃⁺ (r_SCl = 196.2 ± 1.1 pm ?SCl₂ = 102.34 ± 1.13°) and octahedral UCl₆^? ions (r_UCl = 251.1 ± 2.6 pm).     

Die Reaktion von 1,2-Epoxy-octan mit 2-Dimethylamino-äthanol

2-Dimethylaminoethanol reacts with 1,2-epoxyoctane presumably via a hydrogen-bonded complex to form a quaternary ammonium compound which exhibits a fair stability at lower temperatures. At higher temperatures the quaternary structure decomposes with the resulting formation of a wide variety of products. Most of the products have been identified and a reasonable mechanistic picture for their formation is presented. The main products of the reaction are 1-(ß-dimethylaminoethoxy)-2-octanol (IIIa) and 1-dimethylamino-2-octanol (IV), the latter being formed according to several pathways concurrently with ethylene oxide, 2-methyl-4-hexyl-1, 3-dioxolane (VI), and 2-hexyl-1, 4-dioxane (VII). Some of the higher molecular weight products are secondary products resulting from the action of epoxide on the primary reaction products IIIa and IV. The relative amount of each product formed depends on the ratio of starting materials and reaction temperature. In the presence of an additional hydroxylic solvent such as ethanol, the solvent enters also into the reaction.     

Die spektralphotometrische Bestimmung und die Reaktion von Uranylionen mit 4-(2-Thiazolylazo)-resorcin (TAR)

Ohne Zusammenfassung     

Komplexbildung und Extraktion von Molybdän(VI) mit zweizähnigen Liganden

Coordination and Extraction of Molybdenum(VI) with Bidentate Ligands A series of bidentate ligands as well as their thio derivatives from the groups of 8-quinolinols, β-diketones, acylpyrazolones, and N-acyl-phenylhydroxylamines was studied for the ability to extract molybdenum(VI) from heptamolybdate. The extraction principally runs only in acidic medium, sulfur-containing extractants having no advantage. The composition of the complexes was determined by the isolation of compounds in the solid state and also by the interpretation of distribution data.     

Die Diels-Alder Reaktion von Furan und 2-Methylfuran mit Acrylnitril

Diels-Alder reaction between furan or 2-methylfuran and acrylonitrile furnished the expected adducts in good yields. The ratio of the various products was determined.     

Die Reaktion von Eisen(III) mit Brenzkatechin-3,5-disulfonsäure (Tiron) und Äthylendiamintetraessigsäure

The Reaction of Iron(III) with Catechol-3,5-Disulphonic Acid (Tiron) and Ethylene Diamine-Tetracetic Acid In the system iron(III)-Tiron-EDTA a ternary chelate could be detected besides the well known complexes in a weak acid solution. By means of spectro-photometric measurements under various conditions (concentration of ligands) we found [FeHYL]^4? with λ_max = 555 nm und ε₅₅₅ = 2500 l · mol^?1 · cm^?1. The formation of the ternary chelate is an inner-complex reaction of displacing, in which donor atoms of the EDTA in FeY^? are replaced by Tiron. By graphic methods the equilibrium constants could be calculated from the measurements.     

Die Reaktion von N-Halogensulfonamiden und N-N-Dihalogensulfonamiden mit Phenthiazin

Ohne Zusammenfassung     

Die Reaktion von Halogenboranen mit Chlorcyan,Bromcyan und Isocyaniddichloriden

Zusammenfassung BCl₃, BBr₃ und C₆H₅BCl₂ reagieren mit ClCN und BrCN zu hochhalogenierten Bis(methylenaminoboranen). Isocyaniddichloride vom Typ RNCCl₂ (R=C₆H₅ und C₂H₅) bilden mit BCl₃ und BBr₃ Addukte. Die IR-Spektren der Cyclodiborazanderivate werden zugeordnet. BF₃ reagiert nicht.

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BCl₃, BBr₃ and C₆H₅BCl₂ react with ClCN and BrCN to yeald bis(methyleneaminoboranes). C₆H₅NCCl₂ and C₂H₅NCCl₂ give adducts with BCl₃ and BBr₃. Frequencies in the IR-spectra of the cyclodiborazane derivatives are assigned. No reactions are observed with BF₃.

     

Die Dimerisierung von Di(n-butyl)fluorphosphan und seine Reaktion mit Benzaldehyd

The Dimerization of Di(n-butyl)fluorophosphane and its Reaction with Benzaldehyde The phosphorus atom of organylfluorophosphanes possesses electrophilic as well as nucleophilic properties. This dualistic character decisively determines both their disproportionation and their reaction with aldehydes. The phoshanylphoshorane n-Bu₂P? PF₂(n-Bu)₂, 1 b , has been proved to be the intermediat product of the disproportionation of n-Bu₂PF. In the presence of an equimolar amount of Et₃N an equilibrium exists between 1 b and the monomeric n-Bu₂PF. n-Bu₂PF react with benzaldehyde forming the phosphinitophoshorane n-Bu₂P′? O? CHPh? PF₂(n-Bu)₂, 3 a. Reliable information on the reaction pathway has been obtained by means of crossing experiments.     

Zeit- und temperaturaufgelöste Röntgenpulverdiffraktometrie: Die Reaktion von (NH4)2SnF6 mit Ammoniak

Time and Temperature Resolved in situ X-Ray Powder Diffractometry. The Reaction of (NH₄)₂SnF₆ with Ammonia The thermal decomposition of (NH₄)₂SnF₆ under an atmosphere of ammonia is reported. The complicated reaction paths were illucidated by time and temperature resolved in situ x-ray powder diffractometry. It is shown that this technique is a powerful tool to observe structural changes during reaction. It offers also a valuable access to thermodynamic and kinetic data for solid state and gas phase reactions. (NH₄)₂SnF₆ decomposes under ammonia below room temperature to NH₄F and amorphous SnF₄ · x NH₃. At a temperature of 80°C an intermediate product, (NH₄)₄SnF₈, is formed, which decomposes at 140°C into (NH₄)₂SnF₆ and NH₄F. At 250°C (NH₄)[Sn(NH₃)F₅] and Sn(NH₃)₂F₄ are formed. The latter crystallises C-centered monoclinic with lattice constants a = 844.1(5) pm, b = 630.5(3) pm, c = 520.2(3) pm and b? = 114.02(7)°. At 330°C a further decomposition yields SnF₂(NH₂)₂ with a C-centered monoclinic cell and lattice constants a = 1 069(7), b = 325.3(2), c = 504.8(3) pm and b? = 105.83(7)°. Finally above 500°C tin metal is formed.