Bis(perfluor-n-hexyl)- und Bis(perfluor-n-octyl)cadmium: Darstellung,Eigenschaften, NMR-spektroskopische und massenspektrometrische Untersuchungen

Bis(perfluoro-n-hexyl) and Bis(perfluoro-n-octyl) Cadmium: Preparations, Properties, NMR Spectroscopic and Mass Spectrometric Investigations The perfluoroalkyl cadmium compounds Cd(C₆F₁₃)₂ and Cd(C₈F₁₇)₂ are isolated in pure states as well as complexes with dmf, CH₃CN, glyme, and diglyme. The reaction rate of Cd(R_f)₂ with PhHgCl increases with increasing dissociation, which is established by conductivity measurements. The NMR and the mass spectra are discussed.     

Darstellung,Eigenschaften und Kristallstruktur von Bis(phthalocyaninato)cer(IV)

Preparation, Properties and Crystal Structure of Bis(phthalocyaninato)cerium(IV) The anodic or chemical oxidation with dibenzoylperoxide of solutions of bis(phthalocyaninato)cerate(III) in dichloromethane yields selectively sparely soluble bis(phthalocyaninato)cerium(IV), [Ce(Pc(2-)) 2 ]. Green, monoclinic needles cristallize with a = 18.783(12) Å b = 18.739(16) Å c= 15.618(10) Å ß114.30(7)°; Z = 4; space group C2/c. [Ce(Pc(2–)) 2 ] is a sandwich complex in which the cerium Atom is eightfold coordinated by the isoindole nitrogens of the two staggered convex Pc-rings. The u.v.-vis., m.i.r., f.i.r. and resonance Raman spectra are consistent with the structure.     

Bildung,Eigenschaften und Strukturen von Bis(o-hydroxybenzylidenamin)

Ohne Zusammenfassung     

Bildung, Eigenschaften und Strukturen von Bis(o-hydroxybenzylidenamin)

Ohne Zusammenfassung     

Darstellung und Eigenschaften von Tris(diphenylamino)-phosphin

Preparation and Properties of Tris (diphenylamino) Phosphine The synthesis and some properties of tris(diphenylamino)phosphine are described. Displacement of the chlorine atom is readily achieved by reaction of (Ph₂N)₂PCl with Ph₂NSime₃. Thus tris(diarylamino)phosphine (Ph₂N)₃P is obtained almost in quantitativ yield. The aminolysis reaction of PCl₃ or (Ph₂N)₂PCl with Ph₂NH gives also (Ph₂N)₃P. The properties and structure of the phosphine on basis of spectroscopical and X-ray investigations are discussed.     

Darstellung und spektroskopische Eigenschaften von Nitridophthalocyaninatorhenium(V)

Preparation and Spectroscopical Properties of Nitridophthalocyaninatorhenium(V) Nitridophthalocyaninatorhenium(V) ([ReNPc^2?]) is prepared by the reaction of dirheniumheptoxide with ammoniumiodide in molten 1,2-dicyano-benzene. The diamagnetic complex is chemically und thermically extremely stable. In the Uv-vis spectra the typical π-π*-transitions of the Pc^2? ligand are observed. Extra bands in the solid state spectrum are due to strong excitonic coupling of ca. 2.8 kK. In the resonance Raman spectra the intensity of the Re≡N stretching vibration (v(Re≡N)) at 969 cm^?1 is selectively enhanced by laser excitations above 19.0 kK. v(Re≡N) is a dominant m.i.r. absorption at 976 cm^?1.     

Darstellung,Struktur und Eigenschaften von Kupfer(II)-Carbonat

Synthesis, Structure, and Properties of Cupric Carbonate CuCO₃ can be prepared from azurite, malachite or CuO by reaction with CO₂ using a pressure of 20 kb at a temperature of 500°C. The compound is monoclinic, its spacegroup is Pa? C (Nr. 7); the lattice constants are: a = 6.092, b = 4.493, c = 7.030 Å, β = 101.34°. From the structure determination follows the coordination number 5 with a distorted square pyramid of oxygen around the metal. The IR sepctrum ist explained on the basis of site-symmetry considerations.     

Darstellung und Eigenschaften von Kupfer(II)-Hypophosphit

Thermal Behaviour of the Mixtures Na₂S? P₄S₁₀ and Na₄Ge₄S₁₀? P₄S₁₀ of the System Na₂S? GeS₂? P₄S₁₀ The mixtures of Na₂S? P₄S₁₀ and Na₄Ge₄S₁₀? P₄S₁₀ were investigated by DTA and DSC. In the system Na₂S? P₄S₁₀ the congruently melting compounds Na₃PS₄ and (NaPS₃)_x and the peritectic phase Na₄P₂S₇ were found. The IR-spectra are given. Glassy, anhydrous and hydrated Na₄Ge₄S_l0 were prepared and thermochemically characterized. The section Na₄Ge₄S₁₀? P₄S₁₀ is not quasibinary, the mixed cage-anion Ge_4?xP_xS₁₀^(4?x)? thus cannot be prepared by heating and annealing mixtures of Na₄Ge₄S₁₀ and P₄S₁₀.     

Darstellung und Eigenschaften von Vanadyl(IV)-Saccharinat

Summary The synthesis of a new vanadyl(IV)/saccharin complex is reported. Its bonding characteristics differ considerably from all known divalent metal-saccharinates. In this complex a VO(OH)⁺ moiety is coordinated to a saccharin molecule through its carbonyl oxygen and to a saccharinate ion through its deprotonated nitrogen. Two water molecules complete the coordination sphere. X-ray powder diagrams, infrared- and electronic absorption-spectra were recorded and analyzed for the characterization of the compound and its coordination properties. Besides, the magnetic susceptibility and the thermal behaviour were also investigated.

     

Darstellung und Eigenschaften von Trimethyl-(dialkylamidosulfonyl)-ammoniumhalogeniden

Zusammenfassung Aus Dialkylamidosulfochloriden oder-bromiden und Trimethylamin werden thermisch stabile kristalline 11-Additions-verbindungen (Tab. 1) erhalten, die auf Grund von IR-Spektren due Sulfonylammonium-Struktur [R₂NSO₂N(CH₃)₃]⁺ X ^– besitzen. Verglichen mit den zugrunde liegenden Sulfohalogeniden sind sie durch eine erhöhte Reaktionsfähigkeit der Halogenatome gekennzeichnet. Beschrieben werden die Thermolyse und die Reaktionen dieser Verbindungen mit einigen protonenaktiven Stoffen (Wasser, Äthanol, Phenol, Thiophenol). Mit Hexamethyldisilazan liefern sie N,N-Dialkyl-N-trimethylsilylsulfamide, während die freien Sulfohalogenide auch bei erhöhter Temperatur nicht mit dem Disilazan reagieren.

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Synthesis and properties of trimethyl-(dialkylamidosulphonyl)-ammonium halides

Treatment of dialkylamidosulphonyl chlorides or bromides with trimethylamine affords stable crystalline 11 addition compounds of the general formula [R₂NSO₂N(CH₃)₃]⁺ X ^– (cf. Table 1). Evidence for this formulation is obtained from IR spectra. A striking difference between these compounds and the parent sulphonyl halides is the enhanced reactivity of the halogen groups. The thermal degradation and the reactions of the complexes with water, ethanol, phenol, thiophenol, and hexamethyldisilazane are reported. The latter reaction yields N.N-dialkyl-N-trimethylsilyl sulphamides, whereas the corresponding free dialkylamidosulphonyl chlorides are recovered unchanged from refluxing hexamethyldisilazane.

     

Darstellung und Eigenschaften von Trifluormethylmercaptothiophosphoryldichlorid

Preparation and Properties of Trifluoromethylmercaptothiophosphoryldichloride The reaction of CF₃SP(O)Cl₂ with SPCl₃ leads to a CF₃S-chlorine exchange and gives CF₃SP(S)Cl₂ in 50% yield. A controlled hydrolysis of CF₃SP(O)Cl₂ affords CF₃SP(O)(OH)₂, that cannot be isolated as such, but it condenses to CF₃SP(O)(OH)O? [P(SCF₃)(O)? O]_nP(O)(OH)SCF₃. On the other hand, CF₃SP(S)Cl₂ reacts with water to yield H₃PO₄, CF₃SH, S₈, and HCl. CF₃SP(X)Cl₂ reacts with alcohols to give CF₃SP(X)(OR)₂ [R = CH₃, C₂H₅, n-C₃H₇, CH(CH₃)₂, n-C₄H₉ and for X = O, R = C₆H₅, too]. The formation of semi-esters CF₃SP(X)Cl(OR′) could be proven for X = O, R′ = CH₃, C₆H₅ and for X = S, R′ = R. While CF₃SP(O)(OC₂H₅)₂ rapidly decomposes into SCF₂ and FP(O)(OC₂H₅)₂, the other compounds and primarily CF₃SP(O)(OCH₃)₂ and CF₃SP(S)(OR)₂ ar stable. The reaction between CF₃SCl and CH₃SPCl₂ results in CF₃SCH₂SPCl₂ and that between CF₃SP(O)Cl₂ and AlCl₃ gives [CF₃SP(O)Cl]⁺[AlCl₄]^?. Physical and spectroscopical data are given for the newly formed compounds.     

Darstellung und Eigenschaften von Phenyljodcyclopentasilanen

Zusammenfassung Dekaphenylcyclopentasilan reagiert mit wasserfreiem HJ im Bombenrohr unter Benzolabspaltung zu Phenyljodcyclopentasilanen. Der Grad der Phenylabspaltung hängt von der Reaktionszeit ab. Reaktion mit Methanol führt zu entsprechenden Methoxyphenylcyclopentasilanen.Die Hydrolyse ergibt gelbe, fluoreszierende, polymere Hydrolysenprodukte, in denen Si₅-Ringe über Sauerstoff verknüpft sind. Die Farbe der Hydrolysenprodukte wird im Zusammenhang mit den Ergebnissen der Siloxenchemie diskutiert.

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Synthesis and properties of phenyliodocyclopentasilanes

Decaphenylcyclopentasilane reacts with anhydrous HJ in a sealed tube to give phenyliodocyclopentasilanes and benzene, and the degree of phenyl cleavage was found to depend on the reaction time. The corresponding methoxyphenylcyclosilanes are obtained in the reaction with methanol. Hydrolysis yields a yellow, fluorescent, polymeric compound containing Si₅-rings coupled by oxygen. The colour of the hydrolysis products is discussed in connection with pertinent results in siloxene chemistry.

     

Darstellung und Eigenschaften von Organoindiumbromiden

Synthesis and Properties of Organoindium Bromides i-Pr₃In gives with InBr₃ (molar ratio 2:1, toluene, 50°C) i-Pr₂InBr ( 1 ) and (molar ratio 1:2, toluene, 80°C) i-PrInBr₂ ( 2 ). The corresponding reaction of (PhCH₂)₃In and InBr₃ (2:1) gives (PhCH₂)₂InBr ( 3 ), while PhCH₂InBr₂ could be isolated only as ether adduct [PhCH₂InBr₂(OEt₂)_n] ( 4 ). With DME/MeCN and 2 and 4 with THF, respectively, yields the solvate complexes [InBr₃(DME)(MeCN)] ( 5 ), [i-PrInBr₂(THF)₂] ( 6 ) and [PhCH₂InBr₂(THF)₂] ( 7 ). The compounds 1–7 were investigated with NMR-, IR- and MS-techniques. Pyrolysis of the raw material of i-Pr₃In, which contains “MgBrCl” and additional treatment with Et₂O yields the salt [Mg₃Cl_4,65Br_0,35(Et₂O)₆][i-PrInBr_2,7Cl_0,3] ( 8 ). The cation, a trinuclear magnesium complex, possesses local D_3h-symmetric of the Mg₃X₅ backbone (X = Cl, Br).     

Darstellung und Eigenschaften von Carbonylisocyanat

Zusammenfassung Es wird über die erstmalige Darstellung von Carbonylisocyanat, CO(NCO)₂, durch thermische Zersetzung von Trichlorisocyanursäure berichtet; einige physikalische Eigenschaften der neuen Verbindung werden mitgeteilt. Ihre Reaktionen mit Alkali, Wasser, Ammoniak und Äthanol wurden untersucht. Durch Reaktion mit Wasser im Verhältnis 1: 1 wurde 2,4,6-Trioxo-tetrahydro-1,3,5-oxadiazin bzw. Carbonyldicarbamidsäureanhydrid als neue Verbindung erhalten.

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Carbonyl isocyanate has been prepared the first time by thermolysis of trichlorisocyanuric acid and some of its physical properties have been determined. Its reactions with alkali, water, ammonia and ethanol have been investigated. By reaction with equimolar amounts of water the novel compound 2,4,6-trioxotetrahydro 1,3,5-oxadiazine (carbonyl-dicarbamic acid anhydride) was obtained.

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Auszugsweise vorgetragen auf der Vortragstagung des VOeCh. am 28. 9. 1965 in Graz.     

Darstellung und Eigenschaften von Bromisocyanat

Zusammenfassung Durch Vakuumthermolyse von Tribromisocyanursäure konnte Bromisocyanat in größeren Mengen dargestellt werden. Eine genauere Charakterisierung der bereits an anderer Stelle beschriebenen Verbindung sowie ein Vergleich mit den Eigenschaften von Chlorisocyanat werden gegeben.

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Preparation and properties of bromo isocyanate

Bromo-isocyanate has been prepared by vacuum thermolysis of tribromo-isocyanuric acid. A more exact characterization of this just elsewhere described compound and a comparison with chloro-isocyanate are given.

     

Darstellung,Eigenschaften und elektronische Raman-Spektren von Bis(chloro)phthalocyaninatoferrat(III), -ruthenat(III) und -osmat(III)

Preparation, Properties and Electronic Raman Spectra of Bis(chloro)-phthalocyaninatoferrate(III), -ruthenate(III) and -osmate(III) Bis(chloro)phthalocyaninatometalates of Fe^III, Ru^III and Os^III [MCl₂Pc(2-)]^?, with an electronic low spin ground state are formed by the reaction of [FeClPc(2-)] resp. H[MX₂Pc(2?)] (M = Ru, Os; X = Cl, I) with excess chloride in weakly coordinating solvents (DMF, THF) and are isolated as (n-Bu₄N) salts. The asym. M? Cl stretch (ν_as(MCl)) is observed in the f.i.r. at 288 cm^?1 (Fe), 295 cm^?1 (Ru), 298 cm^?1 (Os), ν_as(MN) at 330 cm^?1 (Fe), 327 cm^?1 (Ru), and 317 cm^?1 (Os); only ν_s(OsCl) at 311 cm^?1 is resonance Raman (r.r.) enhanced with blue excitation. The m.i.r. and FT-Raman spectra are typical for hexacoordinated phthalocyanines of tervalent metal ions. The UV-vis spectra show besides the characteristic π-π* transitions (B, Q, N, L band) of the Pc ligand a number of extra bands at 12–15 kK and 18–24 kK due to trip-doublet and (Pc→M)CT transitions. The effect of metal substitution is discussed. The r.r. spectra obtained by excitation between the B and Q band (λ₀ = 476.5 nm) are dominated by the intraconfigurational transition Γ₇ Γ ₈ arrising from the spin-orbit splitting of the electronic ground state for Fe^III at 536 cm^?1, for Ru^III at 961 cm^?1 and Os^III at 3 028 cm^?1. Thus the spin-orbit coupling constant increases very greatly down the iron group: Fe^III (357 cm^?1)< Ru^III (641 cm^?1)< Os^III (2 019 cm^?1). The Γ₇ Γ ₈-transition is followed by a very pronounced vibrational finestructure being composed in the r.r. spectra by the coupling with ν_s(MCl), δ(MClN) and the most intense fundamental vibrations of the Pc ligand. In absorption only vibronically induced transitions are observed for the Ru and Os complex at 1 700-2800 rsp. 3100-5800 em^?1 instead of the 0-0 phonon transitions. The most intense lines are attributed to combinations of the intense odd vibrational mo-des at ≈ 740 and 1120 cm^?1 with ν₅(MCI), δ(MClN).     

Darstellung,Kristallstruktur und Eigenschaften von Kaliumhydrogencyanamid

Preparation, Crystal Structure, and Properties of Potassium Hydrogen Cyanamide For the preparation of KHCN₂ melamine has been reacted with potassium amide in liquid ammonia. After evaporation of the solvent the resulting solid has been transformed at 210°C. KHCN₂ (P2₁2₁2₁, a = 708.7(2), b = 909.0(2), c = 901.4(2) pm, Z = 8, R = 0.039, wR = 0.016) is yielded as a coarse crystalline product. In the solid K⁺ and HCN ions occur. As expected two significantly differing bond-distances C? N (117.3(5) pm) and HN? C (128.7(5) pm) have been found in the anion. According to IR-spectroscopy a non linear group N? C? N (174.4(4)°) is observed.     

Darstellung und Eigenschaften von Aminodisilanen

Zusammenfassung Aus der Klasse der teilweise substituierten Aminodisilane wurden vier Vertreter der Dimethylaminomethyldisilane erstmals hergestellt und durch Analyse, Molrefraktion, UV-,¹H-NMR-, IR- und Ramanspektren charakterisiert.

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Preparation and properties of amino disilanes

Four dimethylamino-methyldisilanes have been prepared and characterized by analysis, molar refraction, UV,¹H-NMR, IR and Raman spectra.