Synthese und Strukturen von Bis(amino)germa- und -stanna-Chalkogeniden

Synthesis and Structures of Bis(amino)germa and -stanna Chalcogenides The cyclic bis(amino)germylene 1 and the -stannylene 2 react with elemental S, Se and Te to yield oxydation products of the general formula Me₂Si(NtBu)₂MEl₂M(NtBu)₂SiMe₂ (M = Ge, El = S ( 4 ), El = Se ( 5 ), El = Te ( 6 ); M = Sn, El = Se ( 9 ), El = Te ( 10 )). As may be deduced from X-ray structures ( 4, 5, 6, 9, 10 ) all compounds show similar central skeletons: the three spirocyclicly connected four-membered rings SiN₂M (2x) and MEl₂M are oriented in an orthogonal way to oneanother. The germanium and the tin atoms thus are in a distorted tetrahedral coordination while the chalcogen atoms only have two neighbours in acute angles. If 1 is allowed to react with trimethylamine-N-oxide, the oxygen is transferred to germanium and [Me₂Si(NtBu)₂GeO]₃ ( 3 ) is formed. Contrarily to the other compounds 3 can be described as a trimer. There is a central almost planar Ge₃O₃ six-membered ring, the germanium atoms serving as spiro-cyclic centres to three GeN₂Si four-membered rings (X-ray structure of 3 ). In the central four-membered rings of 4, 5, 6, 9 and 10 no transanular bonding between the chalcogen atoms have to be considered although these atoms have small distances to oneanother. The mean M-El distances have been found to be: Ge? O 1.762(5), Ge? S 2.226(3), Ge? Se 2.363(3), Ge? Te 2.592(5), Sn? Se 2.536(3), Sn? Te 2.741(3) Å.     

Zur Kenntnis cyclischer Acylale, 3. Mitt.: Zur Elektronenstruktur cyclischer Acylale

Zusammenfassung Mit Hilfe der einfachen LCAO-MO-Methode werden die -Elektronenstrukturen von cyclischen Acylalen der Methylenmalonsäure, Alkylester der Acrylsäure sowie derjenigen Anionen, die durch Angriff einer Anionenbase am -C-Atom des , -ungesättigten Carbonylsystems entstehen, berechnet. An Hand der Ergebnisse wird die Titrierbarkeit der cyclischen Acylale der Methylenmalonsäure diskutiert.Mit 2 Abbildungena)1. Mitt.:J. Swoboda, J. Derkosch undF. Wessely, Mh. Chem.91, 188 (1960). b)2. Mitt.:Gertrude Adametz, J. Swoboda undF. Wessely, Mh. Chem.92, 802 (1961).     

Zur Reduktion verschiedener Anionen und Kationen in der qualitativen Analyse

Ohne Zusammenfassung     

Cyclische Diazastannylene. XIX. Zur Reaktion eines Bis(amino)germylens, -stannylens und -plumbylens mit Phosphortrichlorid und 2, 3-Dimethyl-1, 3-butadien

Cyclic Diazastannylenes. XIX. Reaction of a Bis(amino)germylene, -stannylene, and -plumbylene with Phosphorus Trichloride and 2, 3-Dimethyl-1, 3-butadiene The cyclic bis(amino)germylene 1 reacts with PCl₃ by a threefold insertion into the P? Cl bonds and forms [Me₂Si(N^tBu)₂Ge(Cl)]₃P( 4 ). 4 crystallizes in the triclinic space group P1 with cell dimensions: a = 1955.2(9), b = 1378.3(6), c = 1074.3(5) pm, α = 90.4(1), β = 121.6(1), γ = 97.9(1)° and Z = 2. X-ray structure analysis was used to show, that the molecule 4 has approximately C_3h point symmetry. All germanium, chlorine, and silicon atoms are quite accurately situated in a plane, perpendicular to which the GeN₂Si-rings are erected. The only heavy atom which disturbs the mirror symmetry is the phosphorus, which is on the top of a flat pyramide (Ge? P? Ge = 115.0°). Important bond lengths (mean values) are: Ge? P = 231.0(4), Ge? N = 182.4(7), Ge? Cl = 217.9(2) and Si? N = 173.6(7) pm. The unusual nearly planar coordination of the phosphorus atom can be explained by the particular steric requirements of the substituents. PCl₃ oxidizes the tin atom in the bis(amino)stannylene 2 by the formation of Me₂Si(N^tBu)₂SnCl₂ ( 5 ); as additional product originates an amorphous solid of analytical composition (PCl)_n. In contrast to 1 and 2 the lead atom     

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.     

Zur spektralanalytischen Bestimmung von Spuren Silicium und verschiedener Kationen in Cellulose und ihren Estern

Ohne Zusammenfassung     

Zur bildung neuer linearer und cyclischer isopren-dimerer an titan-katalysatoren mit sauerstoff-chelatliganden

L₂ReH₇ (L=PPh₃) reacts with 3,3-dimethylbutene and benzene (the latter being used as solvent) to give the dihydridocyclohexadienyl compound L₂(η⁵-C₆H₇)ReH₂, the X-ray crystal structure of which is reported. With deuteriobenzene, the reaction gives a product which is partially deuteriated at the rhenium atom and in the ortho-positions of the phosphine ligands.     

Zur Reaktion eines Bis(amino)germylens mit Germaniumaziden: Abfangreaktionen von instabilen Germa-Iminen

Reaction of a Cyclic Bis(amino)germylene with Germaniumazides: Trapping-Reactions of Unstable Germa-Imines . The cyclic bis(amino)germylene 1 reacts with different germaniumazides of the type Me₂Si(NtBu)₂Ge(R)N₃ (R = Me ( 2 ), tBu ( 3 ), N(SiMe₃)₂ ( 4 ), R = N₃ ( 5 )). With the exception of 4 all azides lose dinitrogen when treated with 1 and the Ge^II center coordinates the α-nitrogen of the azide group. It seems to be reasonable to assume a transient germaimine (nitride) which is trapped by further reaction with the azide molecules 2 and 5 or by reaction with the solvent pyridine ( 3 ). In the case of 2 the germatetrazole [Me₂Si(NtBu)₂]GeN₄[Ge(NtBu)₂SiMe₂]₂ ( 6 ) is formed, the tetrazole nitrogens being exclusively substituted by germanium atoms (point symmetry of the molecule C_s(m)). When 1 is treated with 5 a tris(germa)amine [Me₂Si(NtBu)₂Ge(N₃)]₃N ( 8 ) is formed, which has an azide group attached to each Ge-atom. X-ray analysis reveals that the nine nitrogen atoms of the azide groups are coplanar with the trigonal planar Ge₃N moiety (crystallographic symmetry: 3/m). The reaction of 1 with 3 is very surprising: the pyridine in the product Me₂Si(NtBu)₂Ge(C₅H₄N)? N(H)Ge(tBu)(NtBu)₂SiMe₂ ( 7 ) is bonded via an α-carbon atom while the remaining hydrogen has added to the nitride-nitrogen. 6 crystallizes in the monoclinic system space group C2/m, a = 24.306(9), b = 10.933(6), c = 19.420(9) Å, β = 91.81(2)° and Z = 4. 7 crystallizes in the hexagonal system space group P6₃/m with a = b = 16.73(1), c = 11.006(8) Å, γ = 120° and Z = 2, and 8 crystallizes in the monoclinic system space group P2₁/n, a = 11.341(6), b = 26.086(9), c = 13.244(7) Å, β = 98. I2(2)° mit Z = 4.     

Bis[bis(trimethylsilyl)amino]sulfan 1. Darstellung und Charakterisierung

Inhaltsübersicht. Die Titelverbindung[(CH₃)₃Si]₂N–S–N[Si(CH₃)₃]₂ wurde durch Reaktion von Lithium-bis(trimethylsilyl)arnid mit Schwefeldichlorid hergestellt. Elektronenabsorptions-, Infrarot-, Kernresonanz- (¹H, ¹³C, ²⁹Si, ¹⁵N) und Massenspektren werden mitgeteilt. Die Reaktivität der Verbindung wurde untersucht. Bis[bis (trimethylsilyl) amino] sulfane. 1. Synthesis and Characterization Abstract, The title compound [(CH₃)₃Si]₂N–S–N[Si(CH₃)₃]₂ has been prepared by reaction of lithium bis(trimethylsilyl)amide with sulfur dichloride. Electron absorption, infrared, nuclear magnetic resonance (¹H, ¹³C, ²⁹Si, ¹⁶N), and mass spectra are given. The reactivity of the compound has been studied. Im Zusammenhang mit unseren Untersuchungen [1–3] über S-Bis(trimethyl-eilyl)aminoester von Dithiocarbamidsäuren RR′N–CS–S–N[Si(CH₃)₃]₂ haben wir uns mit dem Bis[bis(trimethylsilyl)amino]sulfan [(CH₃)₃Si]₂N-S-N[Si(CH₃)₃]₂ befaßt. Diese Verbindung wurde erstmals 1962 von Wannagat u. Kückertz [4] hergestellt und kurz beschrieben. Wolmershäuser u. Mitarb. [5] teilten einige wenige spektroskopische Daten mit; vgl. auch [6, 7].     

Zur Kenntnis der Bis(dialkylamino)acyloxiborane

About Bis(dialkylamino)acyloxyboranes By reactions of bis(dialkylamino)bromoborane with potassium, lead, silver or trialkylammonium salts of corresponding carboxylic acids the above listed compounds have been prepared. Some properties of the compounds are described.     

Titankomplexe offenkettiger und cyclischer arsanliganden: synthese und katalytische wirkung (1)

The Ti(IV) complexes 1b, 2b, and 6 have been synthesized from new multi-electron ligands. 2b, after reduction with Et₂AlCl, dimerizes isoprene mainly to 8c and trimerizes butadiene mainly to ttt-CDT. Ti(IV) compounds of the macrocyclic ligands 7a-c exhibit the same catalytic properties after reduction with Et₂AlCl.     

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

Ohne Zusammenfassung     

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

Ohne Zusammenfassung