Reaktionen subvalenter Verbindungen des Siliciums mit Stickstoffheterocyclen

Reactions of Subvalent Compounds of Silicon with Nitrogenheterocycles Subvalent compounds of silicon were prepared from dichloro-bis(diethylamino)silane with Na/K alloy in hexane-dimethyloxyethane containing pyridine, 4, 4′-bipyridine, indole, chinoline, lepidine, isochinoline, mono-, di- or trimethylpyridine, N-methylindole or benzofurane. Products isolated from the reaction mixtures are formed either by the insertion of a Si(NEt₂)₂ unit (i) into a CH bond of methyl groups to give silanes RSi(NEt₂)₂H (with N-methylindole, sym-collidine), (ii) into a CN bond of the heterocycle expanding the six membered ring by one unit to give silazepines, or (iii) by the addition of a ClSi(NEt₂)₂ unit to the nitrogen atom of the aromatic heterocycle, which results in 1, 4-dihydro(chlorosilyl)pyridine derivatives. In the silazepines lithiation and subsequent reaction with (CH₃)₃SiCl occurs on a CH- or CH₂ group of the ring. Most compounds are characterized by elemental analyses, n.m.r. (¹H, ¹³C and ²⁹Si) and mass spectra; some have been identified by high resolution mass spectrometry and (or) characteristic signals in their n.m.r. spectra. X-ray structure analyses are provided for V and XX .     

Koordinationsverbindungen von Aminoacridin-N-oxiden mit Metallthiocyanaten der 3d-Reihe

Coordination Compounds of Aminoacridine-N-oxides with Thiocyanates of the 3d Metals . Reactions of thiocyanates of the 3d metals with selected aminoacridine-N-oxides in homogeneous dilutions of N,N-dimethylformamide form compounds of the type [M(AAcNO)_a(DMF)_b(NCS)₂] · cDMF and [M′(AAcNO)_d(DMF)_e(NCS)₃] · fDMF, M = Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺; M′ = Cr³⁺, Fe³⁺; AAc^INO = 3,6-diamino-2,7-dimethylacridin-N-oxide, AAc^IINO = 3,6-bis(dimethylamino)acridin-N-oxide, AAc^IIINO = 2-ethoxy-6,9-diaminoacridin-N-oxide; a = 1, 2, 3, 4; b = 0, 1; c = 0, 1, 2, 3; d = 1, 2, 3; e = 0, 1, 2; f = 0, 1, 2, 3. The complexes are characterized by IR (4000–200 cm^?1) and UV-VIS spectra in solutions and solids and by EPR and conductivity investigations.     

Koordinationsverbindungen des zweiwertigen Nickels und dreiwertigen Kobalts mit Äthylendiimino-bis-acetylaceton

The preparation of compounds with formula Ni(enac ₂) and [Co(enac ₂)L ₂]X is reported [H₂(enac ₂)=ethylenediimino-bis-acetylacetone, C₁₂H₂₀N₂O₂,L=NH₃,py, -pic, diethylamine;X=Cl^–, ClO _– ⁴ , B(C₆H₅) _– ³ ]. The complexes have been studied by means of magnetic susceptibility measurements, infrared, electronic and NMR spectra and conductivity measurements.     

Koordinationsverbindungen von Phenylphosphoroxyhalogeniden mit Akzeptorhalogeniden

Zusammenfassung Es werden Koordinationsverbindungen von sowohl Phenyl-phosphoroxydichlorid als auch Phenylphosphoroxydifluorid mit BF₃, BCl₃, SnCl₄, TiCl₄ und SbCl₅ beschrieben. Auf Grund der Infrarotspektren erfolgt die Koordination über die P=O-Gruppe an das Akzeptorhalogenid. Phenylphosphoroxydifluorid ist ein schwächerer Donor als Phenylphosphoroxydichlorid; gegenüber beiden nimmt die Bindungsstärke folgendermaßen ab: SbCl₅> TiCl₄ SnCl₄.

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Coordination compounds of both phenylphosphonic dichloride and phenylphosphonic difluoride have been obtained with BF₃, BCl₃, SnCl₄, TiCl₄ and SbCl₅. Coordination is achieved between the P=O-group and the acceptor halide as is shown by infrared evidence. Phenylphosphonic difluoride is a weaker donor than phenyl-phosphonic dichloride; the bond strength decreases from SbCl₅> TiCl₄ SnCl₄.

     

Das Atomgewicht des Siliciums

Ohne Zusammenfassung     

Einige Pentafluorphenylderivate des Siliciums

Zusammenfassung Durch Reaktion von SiHCl₃ mit C₆F₅MgCl entsteht (C₆F₅)₃SiH, das durch Chlorierung zum (C₆F₅)₃SiCl und durchWurtz-Synthese zum Disilan (C₆F₅)₃SiSi(C₆F₅)₃ weiterreagiert. An Hand der SiH-Schwingung des Silans und der chemischen Eigenschaften des Disilans wird die elektronenziehende Wirkung des C₆F₅-Substituenten auf das Si und die Schwächung der SiSi-Bindung demonstriert.

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(C₆F₅)₃SiH, formed by the reaction of HSiCl₃ and C₆F₅MgCl, reacts with chlorine to give (C₆F₅)₃SiCl. The latter in aWurtz reaction yielded the disilan (C₆F₅)₃SiSi(C₆F₅)₃.The electron-withdrawing effect of the C₆F₅-group on the silicon atom and the weakening of the Si–Si-bond is demonstrated by the Si–H valence vibration and the chemical properties of the disilane.

     

Bestimmung des Siliciums in Ferrosilicium

Ohne Zusammenfassung     

Ueber die Analyse des Siliciums

Ohne Zusammenfassung     

Zur Bestimmung des Siliciums im Eisen

Ohne Zusammenfassung     

Bestimmung des Siliciums im Eisen und Stahl

Ohne Zusammenfassung     

Über En-dioläther des Siliciums

The reaction of endiolates with dimethyldichlorosilane yields a new heterocyclic system in which a carbon double bond is next to a Si?O linkage. Neither in the cyclic nor in similar open chains an interaction between the two π-systems has been found by Raman spectroscopy.     

Neue Isocyanato- und Isothiocyanatoderivate des Siliciums

The preparation of the new silanes HSi(NCO)₃ and HSi(NCS)₃ from trihalosilanes and silver halogenoides is described. Based on vibrational and nmr spectroscopic arguments the inductive effect of the NCO- and NCS-groups is discussed. The mixed compounds HSiX ₂(NCO) (X=Cl, Br, I), HSiX(NCO)₂ (X=Cl, Br, I), H₂SiCl(NCO), HSiX ₂(NCS) (X=Cl, Br) and HSiCl(NCS)₂ are prepared by halogen/halogenoid exchange reactions and are characterized spectroscopically.