Darstellung und Eigenschaften einiger Hexamethylcyclohexasilanderivate

Starting from hexamethylhexaphenylcyclohexasilane, some new hexamethyl-cyclohexasilane derivatives (Cl, Br, OCH₃, F) were prepared by exchange of the phenyl groups and characterized by analytical and spectroscopic methods.

Herrn Prof. Dr. mult.Victor Gutmann zum 65. Geburtstag gewidmet.     

Darstellung und Eigenschaften einiger Monoarylthalliumbis-dithiocarbamate und -xanthogenate

Synthesis and Properties of Some Monoarylthalliumbisdithiocarbamates and -xanthates The synthesis and properties of some compounds of the general formula R? T and are described. Crystalline substances were obtained, which can be characterized excellently by NMR spectroscopy. Reactions and NMR data are discussed.     

Darstellung und Eigenschaften einiger Hochchlorierter Oligosilane

Preparation and Properties of Some Highly Chlorinated Oligosilanes Tetrakis(trichlorosilyl)silane (neo-Si₅Cl₁₂) is cleaved by HCl in SiCl₄ solution to tris(trichlorosilyl)silane, HSi(SiCl₃)₃, and SiCl₄. HSi(SiCl₃)₃ and bis(trichlorosilyl)silane, H₂Si(SiCl₃)₂, can also be prepared in good yield by reaction of the methoxy compounds HSi[Si(OCH₃)₃]₃ and H₂Si[Si(OCH₃)₃]₂ with BCl₃. The mass, ¹H-n.m.r., and vibrational spectra of HSi(SiCl₃)₃ and H₂Si(SiCl₃) as well as some ¹H-n.m.r. data of HClSi(SiCl₃)₂, HCl₂SiSiCl₃ and H₂ClSiSiCl₃ are reported and discussed. An improved synthesis for neo-Si₅Cl₁₂ is given.     

Darstellung und Eigenschaften einiger methoxylierter Oligosilane

Preparation and Properties of Some Methoxylated Oligosilanes Tetrakis(trichlorsilyl)silane reacts with methanol and triethylamine to tetrakis(trimethoxysilyl)silane ( I ) or a mixture of I , tris(trimethoxysilyl)silane ( II ), Bis(trimethoxysilyl)silane ( III ) and tetramethoxysilane, depending on the reaction conditions. II is chlorinated to tris(trimethoxysilyl)chlorosilane ( IV ) by CCl₄, IV can be further methoxylated to tris(trimethoxysilyl)methoxysilane ( V ). The compounds I–V are characterized by vibrational, ¹H-nmr-, u.v.- as well as mass spectra.     

Darstellung und spektroskopische Eigenschaften einiger Perbromierter und periodierter Oligosilane

Preparation and Spectroscopie Properties of Some Perbromo- and Periodooligosilanes The cleavage of octaphenylcyclotetrasilane and decaphenylcyclopentasilane with Iodine, phosphorus pentabromide and bromine and the successive reaction with HBr/AlBr₃ or HI/AlI₃ give n-Si₄Br₁₀, n-Si₅Br₁₂, n-Si₄I₁₀, and n-Si₅I₁₂. Their IR and Raman spectra are discussed with the aid of a normal coordinate analysis. The spectra of the cyclic iodosilanes Si₄I₈, Si₅I₁₀, and Si₆I₁₂, prepared previously [1], are included in the discussion.     

Darstellung und Eigenschaften neuer kationischer Dienyl-isonitril-dicarbonyl-Komplexe des Eisens und Rutheniums

Preparation and Properties of New Cationic Dienyl-isonitrile-dicarbonyl Complexes of Iron and Ruthenium The hydride abstraction from the η⁴-diene isonitrile metal dicarbonyls M(η⁴-dien)(CNR)(CO)₂ (M = Fe, Ru; dien = C₆H₈ cyclohexadiene-1.3; C₇H₁₀ cycloheptadiene-1.3; R = Me, Et) with [Ph₃C]BF₄ lead to the η⁵-dienyl isonitrile dicarbonyl metal cations [M(η⁵-dienyl)(CNR)(CO)₂]⁺ [dienyl = cyclohexa-2.4-dien-1-yl (C₆H₇), cyclohepta-2.4-dien-1-yl (C₇H₉)]. [Fe(η⁵? C₈H₉)(CNMe)(CO)₂]⁺ (C₈H₉ = bicyclo[5.1.0]octa-3.5-dien-2-yl) is formed by protonation of Fe(η⁴? C₈H₈)(CNMe)(CO)₂ (C₈H₈ = COT) under valency isomerization. The two cations [Fe(η⁵? C₇H₉)(CNMe)(CO)₂]⁺ and [Fe(η⁵? C₈H₉)(CNMe)(CO)₂]⁺ can be deprotonated with NEt₃ to the neutral cycloheptatriene respectively COT complexes Fe(η⁴? C₇H₈)(CNMe)(CO)₂ and Fe(η⁴? C₈H₈)(CNMe)(CO)₂. The temperature dependent ¹³C-NMR spectra of [Fe(η⁵? C₇H₉)(CNMe)(CO)₂]⁺ and [Ru(η⁵? C₆H₇)(CNMe)(CO)₂]⁺ show the fluctional behaviour of these cations in solution. At low temperatures one CO group occupies the apical position of a square pyramid whereas the isonitrile ligand, the other CO group and the dienyl part are in the basal positions. The ΔG values of the CP exchange points out a higher activation energy as in the corresponding η⁴-diene metal complexes.     

Darstellung und Eigenschaften neuer Tris(fluoraryl)borane

Preparation and Properties of New Tris(fluoroaryl)boranes B(2-FC₆H₄)₃, B(4-FC₆H₄)₃, B(2,6-F₂C₆H₃)₃ and B(C₅F₄N)₃ are prepared from the reactions of RMgX with boron trifluoride, B(OC₆F₅)₃ and B(SC₆F₅)₃ from C₆F₅XH (X = O, S) and boron trichloride. The synthetic routes and the properties of these mainly new compounds are described.     

Über Darstellung und Eigenschaften einiger cyclischer und polymerer Trithiokohlensäureester

Zusammenfassung Durch direkte Umsetzung von Schwefelkohlenstoff mit aliphatischen oder araliphatischen Dithiolen in Gegenwart von tertiären Aminen und Blei(II)-Ionen lassen sich in einem Reaktionsschritt je nach der Zahl der Kohlenstoffatome zwischen den Mercaptogruppen cyclische oder polymere Ester der Trithiokohlensäure erhalten. Es wird über deren Eigenschaften und Spektren berichtet. Die dargestellten Poly-trithiocarbonate werden mit den aus Thiophosgen und Dithiolen entstehenden Polymeren verglichen.

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In a direct one-step reaction of carbon disulfide with aliphatic or araliphatic dithiols in the presence of tertiary amines and lead(II)-ions cyclic or polymeric esters of trithiocarbonic acid, depending on the number of carbon atoms between the mercapto groups, can be obtained. The properties and spectra of the esters are reported. The poly-trithiocarbonates prepared are compared with the polymers made from thiophosgene and dithiols.

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Mit 3 Abbildungen     

Darstellung und Eigenschaften einiger Bis- und Tris(diphenylphosphino)di-, tri- und tetrasilane

Dimethyldichlorosilane, 1,2-dichlorotetramethyldisilane, 1,3-dichlorohexamethyltrisilane and methyltris(chlorodimethylsilyl)silane react with diphenylpotassiumphosphide. The resulting bis- and tris(diphenylphosphino)silanes are characterized by IR and²⁹Si as well as³¹P-NMR-spectroscopy.

     

Darstellung und Eigenschaften einiger Molybdän(II)-Thiocarboxylate

Preparation and Properties of Some Molybdenum (II) Thiocarboxylates The binuclear thiocarboxylates Mo₂(CH₃COS)₄, Mo₂(COS)₄, and Mo₂(C₆H₅CSS)₄ have been prepared and characterized by their spectroscopic properties. With the exception of Mo₂(C₆H₅CSS)₄ investigations of vapourization (mass spectrometer) show the binuclear molecules in the vapour phase. For the u. v.- and i. r.-spectra an assignment of the observed bands is given. The magnetic measurements of the three compounds show no systematic differences.     

Darstellung und Eigenschaften einiger Nickel(0)-Komplexe mit stickstoffhaltigen Alkinverbindungen

Preparation and Properties of Some Nickel(0) Complexes with Nitrogen-containing Acetylenic Compounds Compounds of the type (ligand)₂Ni(acetylene) have been prepared by reactions of complexes (ligand)₂Ni(C₂H₄) with disubstituted nitrogen-containing acetylenes. The new complexes are characterized by some chemical reactions and physical methods and compared with recently prepared hydroxy-acetylene compounds.     

Trivalent-pentavalente Phosphorverbindungen/Phosphazene. IV. Darstellung und Eigenschaften neuer N-silylierter Diphosphazene

Trivalent-Pentavalent Phosphorus Compounds/Phosphazenes. IV. Preparation and Properties of New N-silylated Diphosphazenes Phosphazeno-phosphanes, R₃P = N? P(OR′) ₂ (R = CH₃, N(CH₃)₂; R′ = CH₂? CF₃) react with trimethylazido silane to give N-silylated diphosphazenes, R₃P = N? P(OR′)₂ = N? Si(CH₃)₃ compounds decompose by atmospherical air to phosphazeno-phosphonamidic acid esters, R₃ P?N? P(O)(O? CH₂? CF₃)(NH₂). Thermolysis of diphosphazene R₃P = N? P(OR′) ₂ = N? Si(CH₃)₃ (R = CH₃, R′ = CH₂? CF₃) produces phosphazenyl-phosphazenes [N?P(N?P(CH₃)₃)OR′] _n. The compounds are characterized by elementary analysis, IR-, ¹H_-, ²⁹Si-, ³¹P-n.m.r., and mass spectroscopy.     

Darstellung und eigenschaften neuer monosilylcyclopentasilanderivate

New SiMe₂R-substituted derivatives of decamethylcyclopentasilane were prepared by different pathways. The halogen compounds where R = F, Cl, Br or I exhibit a strong influence of the substituent on the physical properties of the silicon ring. Hydrolysis of the halides gives a hydroxy compound (R = OH) and takes place extremely slowly, whereas the formation of polysiloxanes is favoured.     

Synthese und Eigenschaften einiger Phenoxyarylsilane

Ohne Zusammenfassung     

Synthese und Eigenschaften einiger Iodtrisilane

The syntheses and properties of the iodotrisilanes (IH₂Si)₂SiH₂, (IH₂Si)₂SiHI, I₃SiSiI₂SiH₃, (I₃Si)₂SiH₂ and Si₃I₈ are reported. All trisilanes were synthesized from the appropriate phenyltrisilanes and hydrogen iodide, with the exception of I₅Si₃H₃, which was prepared by thermolysis of I₃SiSiH₃. The ²⁹ Si-chemical shifts and ²⁹Si²⁹Si-coupling constants are reported. ab]Die Synthesen und Eigenschaften der Iodtrisilane (IH₂Si)₂SiH₂, (IH₂Si)₂SiHI, I₃SiSiI₂SiH₃, (I₃Si)₂SiH₂ und Si₃I₈ werden beschrieben. Bis auf I₅Si₃H₃, das während der Thermolyse von I₃SiSiH₃, entstand, wurden alle Iodtrisilane aus den entsprechenden Phenyltrisilanen mit Iodwasserstoff hergestellt. Die ²⁹Si-Verschiebungen und ²⁹Si²⁹Si-Kopplungskonstanten werden mitgeteilt.     

Eigenschaften und Zustandsdiagramme einiger silberchalkogenidsysteme

Zusammenfassung Auf Grund einer von uns durchgeführten Untersuchung über die Zustandsdiagramme der Silberchalkogenidsysteme Ag₂Te-Ag₂Se, Ag₂Te-Ag₂S, Ag₂Se-Ag₂S und über die Diagonalquerschnitte Ag₂Se_0.5Te_0.5-Ag₂S, Ag₂S_0.5Te_0.5-Ag₂Se, Ag₂Se_0.5S_0.5-Ag₂Te wurden ein Projektion des Raumdiagramms der Liquidusflachen und einige der wichtigsten isothermen Schnitte des dreidimensionalen Systems Ag₂Te-Ag₂Se-Ag₂S aufgestellt. Nach der Interpretation der Art und Lage der einzelnen Phasen wurden für jedes der Systeme die elektrischen und wärmephysikalischen Eigenschaften bei Temperaturen von der des flüssigen Stickstoffes bis zu den Temperatures des Phasenübergangs untersucht und der thermoelektrische Wirkungsgrad (Z, K^–1) berechnet.

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On the basis of a previous investigation on the phase diagrams of the silverchalcogenide systems Ag₂Te-Ag₂Se, Ag₂Te-Ag₂S and Ag₂Se-Ag₂S and the diagonal sections Ag₂Se_0.5Te_0.5-Ag₂S, Ag₂S_0.5Te_0.5-Ag₂Se and Ag₂Se_0.5S_0.5-Ag₂Te, the projections of liquidus surfaces and more characteristic isothermal sections of the Ag₂Te-Ag₂Se-Ag₂S phase diagram were constructed. After interpretation of the types and situations of the separate phases in each of the systems studied, their electric and thermophysical properties were investigated in the temperature range from 77 K up to the temperatures of the phase transitions and the values of thermoelectric efficiency were calculated,Z, Ksu–1.

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Ag₂Te-Ag₂Se, Ag₂Te-Ag₂S, Ag₂Se-Ag₂S Ag₂Se_0.50.5-Ag₂S, Ag₂S_0.5Te_0.5-Ag₂Se, Ag₂Se_0.5S_0.5-Ag₂Te Ag₂Te-Ag₂Se-Ag₂S. . 77 . .

     

Darstellung und Reaktionen einiger Diphenylwismutalkoxide

Synthesis and Reactions of Some Diphenylbismuth Alkoxides The synthesis and some properties of compounds of the general formula (C₆H₅)₂BiOR are described. Nucleophilic displacement of the aloxy groups is readily achieved by reactions with thiols. Thus sulphur containing organobismuthines of the general formula (C₆H₅)₂BiSR are formed in nearly quantitative yield.