Synthese und Eigenschaften von 1,1,3,3-Tetrakis(pentafluorphenyl)-cyclo-di(silthian) und verwandten Verbindungen

Summary The synthesis of tetrakis(pentafluorophenyl)-cyclo-di(silthiane) and related compounds by reacting organosubstituted silanes with sulfur or hexamethyldisilthiane is reported The compounds are characterized by analysis, by relative molecular mass, by¹H,¹³C,¹⁹F, and²⁹Si NMR spectroscopy, and by mass and IR spectra, respectively. Two²⁹Si NMR signals of different intensity found for compounds with two different organic substituents on silicon are explained by the existence of diastereomers.

     

Synthesen und Eigenschaften von Bis(perfluoralkyl)zink‐Verbindungen

Syntheses and Properties of Bis(perfluoroalkyl)zinc Compounds The conditions for the syntheses of bis(perfluoroalkyl)zinc compounds Zn(R_f)₂ · 2 D (R_f = C₂F₅, n‐C₃F₇, i‐C₃F₇, n‐C₄F₉, n‐C₆F₁₃, n‐C₇F₁₅, and n‐C₈F₁₇; D = CH₃CN, tetrahydrofurane, dimethylsulfoxide) are described. Mass spectra, thermal decompositions, ¹⁹F‐ and ¹³C‐NMR spectra are discussed.     

Synthese und Eigenschaften von Bis(Dimethylarsino)-aminen

Synthesis and Properties of Bis(dimethylarsino) Amines Primary amines react with cacodyl halides (CH₃)₂AsX (X = Cl, J) under formation of Bis(dimethylarsino)amines RN[As(CH₃)₂]₂. Nine amines were prepared. The compounds were characterized by IR, ¹H-nmr and mass-spectroscopy. In the reactions with acid molecules cleavage of the As? N bond was observed. Formation of amine RNH₂ or ammoniumsalt (RNH₃)X and cacodyl derivates took place in all cases. The reactions of the arsinoamines with some carbonyles are reported.     

Synthese und Eigenschaften von Bis(dialkylamino)-methylarsinen

Synthesis and Properties of Bis(dialkylamino)methylarsines The reactions of secondary amines with CH₃AsJ₂ lead to the formation of Bis(dialkylamino)methylarsines. Ten arsines have been prepared by this method and are described. IR and ¹H-NMR and mass spectral data are presented for these compounds and discussed. Acid molecules cleave the As? N bond. The reactions with halogen hydrides, water, alkoholes, thioles and amines are described.     

Synthese und Eigenschaften von (Acido)(nitrosyl)phthalocyaninato(2–)ruthenium

Synthesis and Properties of (Acido)(nitrosyl)phthalocyaninato(2–)ruthenium (Acido)(nitrosyl)phthalocyaninato(2–)ruthenium, [Ru(X)(NO)pc^2–] (X = F, Cl, Br, I, CN, NCO, NCS, NCSe, N₃, NO₂) is obtained by acidification of a solution of bis(tetra(n-butyl)ammonium) bis(nitro)phthalocyaninato(2–)ruthenate(II) in tetrahydrofurane with the corresponding conc. mineral acid or aqueous ammonium salt solution. The nitrite-nitrosyl conversion is reversal in basic media. The cyclic and differential pulse voltammograms show mainly three quasi-reversible one-electron processes at 1.05, –0.65 and –1.25 V, ascribed to the first ring oxidation and the stepwise reduction to the complexes of type {RuNO}⁷ and {RuNO}⁸, respectively. The B < Q < N regions in the electronic absorption spectra are still typical for the pc^2– ligand, but are each split into two strong absorptions (14500/16500(B); 28000/30500(Q); 34500/37000 cm^–1(N)), whose relative intensities strongly depend on the nature of the axial ligand X. In the IR spectra is active the N–O stretching vibration between 1827 (X = I) and 1856 cm^–1 (F), the C–N stretching vibration at 2178 (X = NCO), 2072 (NCS), 2066 (NCSe), 2093 cm^–1 (CN), the N–N stretching vibration of the azide ligand at 2045 cm^–1, the fundamentals of the nitrito(O) ligand at 1501, 932, and 804 cm^–1, and the Ru–X stretching vibration at 483 (F), 332 (Cl), 225 (Br), 183 (I), 395 (N₃), 364 (ONO), 403 (CN), 263 (NCS), and 231 cm^–1 (NCSe). In the resonance Raman spectra, excited in coincidence with the B region, the Ru–NO stretching vibration and the very intense Ru–N–O deformation vibration are selectively enhanced between 580 and 618 cm^–1, and between 556 and 585 cm^–1, respectively.     

Die Synthese und einige Eigenschaften von Hydraziniumfluoroscandaten(III)

The synthesis of N₂H₅ScF₄·0.5 HF·0.5 H₂O, N₂H₅ScF₄, and N₂H₆ScF₅ is described. The thermal properties and infrared spectra of the compounds obtained are discussed. The assignation of the bands in infrared spectra (4000 to 250 cm^?1) of the first two compounds is consistent with the presence of hydrazinium⁺¹ ion and for the third one with the presence of hydrazinium⁺² ion.     

Synthese,Kristallstruktur und Eigenschaften von Vanadium(II)‐tetrachloroaluminat

Synthesis, Crystal Structure, and Properties of Vanadium(II) Tetrachloroaluminate The reaction of vanadium dichloride and aluminium trichloride yields vanadium(II) tetrachloroaluminate. Amber cuboid crystals can be obtained by slow cooling of the melt. V(AlCl₄)₂ crystallizes in the monoclinic space group I2/c (a = 1284.6(3), b = 776.3(2), c = 1163.5(2) pm, β = 92.376(10)°) and is therefore isotypic to Co(AlCl₄)₂. The structure contains chains build of VCl₆ octahedra and AlCl₄ tetrahedra sharing corners and edges with each other. The temperature dependence of the magnetic susceptibility follows Curie‐Weiss behaviour (μ = 3.88(2) μ_B, Θ = ?9(1) K) complying with the spin‐only paramagnetism expected of d³ ions.     

Synthese,Eigenschaften und Struktur von cis-Dihydridoazido-tris(triphenylphosphino)-iridium

Synthesis, Properties, and Structure of cis-Dihydrido Azido Tris(triphenylphosphino) Iridium cis-IrH₂(N₃)(PPh₃)₃ is formed from IrCl₃(PPh₃)₃ and NaN₃ in alcohol. The solvent transfers the hydride ions whereby aldehyde is formed. The creme-colored cis-IrH₂(N₃)(PPh₃)₃ is a diamagnetic low-spin complex. Exposure to light yields H₂ and Ir(N₃)(PPh₃)₃ in a reversible process. The cis position of the hydrido ligands is confirmed by the i.r. and H-N.M.R. spectra. Cis-IrH₂(N₃)(PPh₃)₃ crystallizes in the monoclinic system with the space group P2₁/c. The crystal structure exhibits isolated octahedral complexes, in which one hydrido ligand is located trans to the azido group. The other one being trans to one of the phosphine ligands.     

Trimethylsilylverbindungen der Vb-Elemente. I Synthese und Eigenschaften von Trimethylsilylarsanen

Trimethylsilyl Derivatives of Vb-Elements. I. Syntheses and Properties of Trimethylsilylarsanes Chlorotrimethylsilane and ?Na₃As/K₃As”? prepared from a sodium potassium alloy and arsenic powder in dimethoxyethane form tris(trimethylsilyl)arsane 4 in 80 to 90percent; yield. 4 reacts with methyllithium in THF or dimethoxyethane to lithiumbis(trimethylsilyl)arsenide 5 , which crystallizes with two molecules THF – 5a – or one molecule dimethoxyethane – 5b – per formula unit. The latter adduct is dimeric in benzene. In the reaction of 5 with primary and secondary alkyl halides methyl- 1a , ethyl- 1b , isopropyl- 1c , benzyl- 1d , diphenylmethylbis(trimethylsilyl)arsane 1e and bis[bis(trimethylsilyl)arsano]methane 1f are formed. With tert. butyl chloride a β-elimination results in the formation of bis(trimethylsilyl)arsane; in the reaction with chlorodiphenylmethane and dibromoethane an alkali metal-halogen-exchange takes place yielding tetrakis(trimethylsilyl)-diarsane 6 . On heating bis[bis(trimethylsilyl)arsano]dimethylsilane 7 , synthesized from 5 and dichlorodimethylsilane, to 240°C for several days it decomposes to 4 and dodecamethyl-hexasila-tetra-arsa-adamantane 8 . Tert. butyl- 1g and phenylbis(trimethylsilyl)arsane 1h which cannot be obtained from 5 are prepared from primary arsanes via the corresponding dilithium derivatives.     

Synthese,Eigenschaften und Kristallstruktur des cis-Dichloro-bis(diethyldithiophosphinato)titan(IV)

Synthesis, Properties, and Crystal Structure of cis-Dichloro-bis(diethyldithiophosphinato)-titanium(IV) By reaction of TiCl₄ with dialkyldithiophosphinic acids R₂P(S)SH (R ? CH₃, C₂H₅) red chelates (R₂PS₂)₂TiCl₂ are obtained which are very sensitive to hydrolysis. Crystal structure analysis of the ethyl compound shows a distorted octahedral chromophor TiS₄Cl₂ with cis-configuration.     

Synthese und Eigenschaften einiger neuer Mono(π-cyclopentadienyl)-Nickel-Komplexe

During studies on the mechanism of ligand displacement reactions of nickelocene non-ionic monocyclopentadienylnickel complexes of the type π? C₅H₅Ni[P(OP)₃]X with X = Cl and P(O) (OR)₂ have been obtained. The new compounds have been characterised by means of their IR., UV., NMR. and Mass spectroscopic data. The phosphonate ligands are bonded with the phosphorus atom to the transition metal.     

trans-Bis(triphenylphosphin)phthalocyaninato(2–)rhenium(II): Synthese,Eigenschaften und Kristallstruktur

trans -Bis(triphenylphosphine)phthalocyaninato(2–)rhenium(II): Synthesis, Properties, and Crystal Structure Dirheniumheptoxide reacts with phthalodinitrile in boiling 1-chloronaphthalene and subsequent reprecipitation of the green raw product from conc. sulfuric acid to yield an oxo-phthalocyaninate of rhenium, which is reduced by molten triphenylphosphine forming dark green trans-bis(triphenylphosphine)phthalocyaninato(2–)rhenium(II), ^trans[Re(PPh₃)₂pc^2–]. The latter crystallizes triclinic in the space group P 1 with the cell parameters as follows: a = 11.512(2) Å, b = 12.795(2) Å, c = 12.858(2) Å, α = 64.42(2)°, β = 79.45(2)°, γ = 72.74(1)°; V = 1628.1(5); Z = 1. Re is in the centre of the (N_p)₄ plane (N_p: N1, N3) and coordinates two triphenylphosphine ligands axially in trans position. The average Re–N_p and Re–P distances are 2.007(1) and 2.516(3) Å, respectively. Despite the many extra bands the typical B, Q and N regions of the pc^2– ligand are observed at ca. 16500, 28900/32900 and 35300 cm^–1. A weak band group at ca. 8900 cm^–1 is attributed to a trip-multiplet transition, another one at ca. 14500 cm^–1 to a P → Re charge transfer. The vibrational spectra are dominated by internal vibrations of the pc^2– ligand. The very weak intensity of the IR bands at 905 and 1327 cm^–1 are diagnostic of the presence of Re^II.