Reaktionen von Lithium-Chlor-bis(trimethylsilyl)methan mit Fluorsilanen

Reactions of Lithium-chlor-bis (trimethylsilyl)methane with Fluorosilanes The lithium salt of chloro-bis(trimethylsilyl)methane reacts with fluorosilanes to give monosubstituted compounds ( 1—6 ). The reaction is often accompanied by exchange of the chloro atom by hydrogen ( 3—6 ) and by formation of disubstituted products ( 7—11 ) and Cl₂C(SiMe₃)₂. The lithiation of dichloro-bis(trimethylsilyl)methane may occur in reaction with C₄H₉Li ( 1—4, 6 ) or with elemental lithium ( 5 ). Butylsubstituted compounds were obtained as by products of 6 (6 a) and 10 (10 a) . The unsymetrical SiF-substituted compound 12 is formed in reaction of lithiated 2 with F₂SiMe₂. By absence of F₂SiMe₂ the lithium salt dimerises under formation of a 1, 3-disilacyclobutane and LiF.     

Umsetzungen von Metall- und Metalloidverbindungen mit mehrfunktionellen Molekülen. XV. Umsetzungen von N,O-Bis(trimethylsilyl)acylamiden mit Halogenboranen

Reactions of Metal and Metalloid Compounds with Polyfunctional Molecules. XV. Reaction of N, O-Bis(trimethylsilyl)acylamides with Halogenoboranes N, O-bis(trimethylsilyl) acylamides react with halogenodiorganylboranes to give monomeric iminoboranes, which are in equilibrium with the corresponding monomeric amidoboranes. In several cases we obtained dimeric amidoboranes, which partially are in equilibrium with the monomeric form. ¹H, ¹¹B and ¹⁹F n. m. r. spectra, mass spectra and characteristic i. r. group frequencies are reported.     

Reaktionen von 1,2-Bis(trimethylsilyl)iminen mit Selen-und Tellur-halogeniden

Reactions of 1,2-Bis(trimethylsilyl)imines with Selenium and Tellurium Halogenides The reactions of benzil-bis(trimethylsily)imine and phenanthrene-9,10-bis(trimethylsilyl)imine with SeOCl₂, SeCl₄ and TeCl₄ are described.     

Reaktionen von Zink- und Cadmiumhalogeniden mit Tris(trimethylsilyl)phosphan und Tris(trimethylsilyl)arsan

Reactions of Zinc and Cadmium Halides with Tris(trimethylsilyl)phosphane and Tris(trimethylsilyl)arsane ZnCl₂ reacts with E(SiMe₃)₃ (E = P, As) in toluene in the presence of PⁿPr₃ to give the binuclear complexes [Zn₂Cl₂{E(SiMe₃)₂}₂(PⁿPr₃)₂] · C₇H₈ (E = P 1 , As 2 ). Therefore by the use of PⁱPr₃ clusters consisting of ten metal atoms are obtained, [Zn₁₀Cl₁₂(ESiMe₃)₄(PⁱPr₃)₄] (E = P 3 , As 4 ). As a result of the reaction of CdBr₂ with P(SiMe₃)₃ the compound [CdBr₂{P(SiMe₃)₃}]₂ ( 5 ) can be isolated at –40 °C. In the presence of PⁿPr₃ CdBr₂ reacts with P(SiMe₃)₃ forming the binuclear complex [Cd₂Br₂{P(SiMe₃)₂}₂(PⁿPr₃)₂] · thf ( 6 ). The same reaction with PⁱPr₃ yields to the cluster [Cd₁₀Br₁₂(PSiMe₃)₄{P(SiMe₃)₃}₄] · 2 C₇H₈ ( 7 ). ZnI₂ and CdI₂ react with As(SiMe₃)₃ to yield the complexes [MI₂{As(SiMe₃)₃}]₂ (M = Zn 8 , Cd 9 ). In the case of CdI₂ additionally the cluster [Cd₁₀I₁₂(AsSiMe₃)₄ · {As(SiMe₃)₃}₄] · 4,5 C₇H₈ ( 10 ) is formed which is analogous to the compounds 3 , 4 and 7 . In the presence of [PⁿBu₄]I 8  reacts in THF to give the ionic compound [PⁿBu₄]₂[Zn₆I₆(AsSiMe₃)₄(thf)₂] · C₆H₆ ( 11 ).     

Reaktionen von Gemischtligand-Komplexen des Nickel(0) mit Kohlenstoffdichalcogeniden

Reactions of Mixed Ligand Complexes of Nickel(0) with Carbon Dichalcogenides Decisive for the occurrence of a reaction between mixed ligand complexes of nickel(0) and carbon dichalcogenides is the HOMO-energy of the complex and the LUMO-energy of the reagent, which are reflected in the corresponding polarographic half-wave potentials. Therefore, (dipy)-Ni(COD) is substituted by SeCS, CS₂ and SCO, whereas (PPh₃)₂Ni(C₂H₄) only reacts with CS₂, but not with SCO. Substitution by CO₂ needs substrates like Ni(PCy₃)₃ or Ni(PEt₃)₄ which have the lowest anodic waves. (PCy₃)₂Ni(C₂H₄) and (dipy)Ni(PPh₃)₂ effect C?S-bond breaking in SCO, and mixed carbonyls, such as (PCy₃)₂Ni(CO)₂ or (PPh₃)₂Ni(CO)₂, are formed. Futher products are dithiocarbonates or oligonuclear nickel sulfides which are stabilized by a phosphine. Another oligonuclear complex, (PPh₃)₂Ni₃(CS₂)₂, is formed by the reaction of CS₂ with surplus (PPh₃)₂Ni(C₂H₄). The function of CS₂ is that of a bridging ligand. The carbon dichalcogenides are side-on (η²) coordinated in compounds like (dipy)Ni(CS₂), (PPh₃)Ni(CS₂) and (dipy)Ni(SCO). It is always the highest electronegative heteroatom of the non symmetric ligands SeCS and SCO which does not interact with the central atom.     

Reaktionen von TaCl5, MoCl5 und WCl6 mit Bis(trimethylsilyl) carbodiimid

Reactions of TaCl₅, MoCl₅, and WCl₆ with Bis(trimethylsilyl)carbodiimide When TaCl₅ reacts with Me₃SiNCNSiMe₃ (Me = CH₃) in a 1:1 molar ratio, 1 mol Me₃SiCl and dimeric [Cl₄TaNCNSiMe₃]₂ is formed. The vibrational spectra (IR and Raman) show a planar structure of approximate C_2h symmetry. Polymeric [Cl₄WNCN]_n is formed by the reaction of WCl₆ and Me₃SiNCNSiMe₃, but 2 mol Me₃SiCl result in this 1:1 molar interaction. On the other hand MoCl₅ and Bis(trimethylsilyl)carbodiimide (molar ratio 2:1) forms polymeric [(Cl₄Mo)₂NCN]_n, a compound with Mo? N? Mo and Mo—(Cl₂)—Mo bridges. The IR spectra of these carbodiimide derivatives are used for structural suggestions.     

Reaktionen von dienen mit dem dichlorcarbenreagens von makosza und wawrzyniewicz

Compared to dichlorocarbene from other sources the highly reactive dichloro carbene reagent of Makosza and Wawrzyniewicz gives better yields of bis- und tris-adducts even with compounds lacking activation. Compounds 4, 10, and 11 have been prepared for the first time; Compounds 10 and 11 show unusual long-range couplings between methyl protons 5 bonds apart.     

Kristallstruktur des Bis[lithium-tris(trimethylsilyl)-hydrazids] und Reaktionen mit Fluorboranen, -silanen und -phosphanen

Crystal Structure of Bis[lithium-tris(trimethylsilyl)hydrazide] and Reactions with Fluoroboranes, -silanes, and -phospanes Tris(trimethylsilyl)hydrazine reacts with n-butyllithium in n-hexane to give the lithium-derivative 1 . The reaction of 1 with SiF₄, PhSiF₃, BF₃ · OEt₂, F₂BN(SiMe₃)₂ and PF₃ leads to the substitution products 2–6 . The 1,2-diaza-3-bora-5-silacyclopentane 7 is formed by heating (Me₃Si)₂N? N(SiMe₃)(BFNSiMe₃)₂ ( 5 ) at 250°C. In the reaction of (Me₃Si)₂N? N(SiMe₃)PF₂ ( 6 ) with lithiated tert.-butyl(trimethylsilyl)amine the hydrazino-iminophosphene (Me₃Si)₂N? N = P? N(SiMe₃)(CMe₃) ( 8 ) is obtained. In the molar ratio 2:1 1 reacts with SiF₄ and BF₃ · OEt₂ to give bis[tris(trimethylsilyl)hydrazino]silane 9 and -borane 10 .     

Zur Untersuchung der Reaktionen von Hochpolymeren mit dem Infrarot-Spektrophotometer

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Reaktionen von Schwermetallen mit Thioderivaten des Salicylaldehyds

Ohne Zusammenfassung     

N,O-Bis(trimethylsilyl)acetamide/N-hydroxysuccinimide ester(BSA/NHS) as coupling agents for dipeptide synthesis

A method using N,O-bis(trimethylsilyl)acetamide/N-hydroxysuccinimide ester(BSA/NHS) as coupling agents for dipeptide synthesis is descried. The coupling reaction between N-hydroxysuccinimide(NHS)esters and amines could be performed under mild conditions with N,O-bis(trimethylsilyl)acetamide(BSA) as coupling reagent and no additional acid/base is required. All byproducts and excessive reactants are water soluble or hydrolysable and easy to eliminate through water-washing at the purification stage.Moreover, all the reactants are inexpensive and widely used in conventional drug production.     

N,N-Bis(trimethylsilyl)dithiocarbazinsäure-S-methylester: Darstellung,Struktur und Reaktionen mit Halogenverbindungen des Titans,Niobs, Tantals und Molybdäns

N,N-bis(trimethylsilyl)-S-methyldithiocarbazate. Preparation, Molecular Structure, and Reactions with Titanium, Niobium, Tantalum, and Molybdenum Halides The reaction of Me₃SiCl with NH₂NHC(S)SMe yields as single product the title compound (Me₃Si)₂Nnhc(S)SMe ( 1 ). The Si₂NNC(S)S moiety is not planar. The Si? N-distances are in the range 176.9(8) to 178.1(9) pm. 1 does not react to hydrazido or diazenido complexes with Cp₂TiCl₂, CpTiCl₃, MCl₅ and CpMCl₄ (M = Nb, Ta). With MoO₂Cl₂(dmso)₂ the dimeric compound (dmso)₂Mo(μ-NNC(S)SMe)₂Mo(O)Cl₂ is obtained.     

Reaktionen von Undecacarbonyl(acetonitril)trieisen mit Alkinethern

Reactions of Undecacarbonyl(acetonitrile)triiron with Alkyne Ethers (CO)₁₁(CH₃CN) 1 reacts with the alkyne ethers H₃C? C?C? OC₂H₅ 2a , H? C?C? OC₂H₅ 2b , H₃C? O? CH₂? C?C? CH₂? O? CH₃, 2c and H₃C? O? C(CH₃)H? C?C? C(CH₃)H? O? CH₃ 2d forming different cluster products depending on the substituents and the reaction conditions. The product obtained with 2a is the bisalkylidyne cluster Fe₃(CO)₉(m?₃-C? CH₃)(m?₃-C? OC₂H₅) 3 which results from the cleavage of the carbon carbon triple bond. The alkyne 2b however yields the vinylidene cluster Fe₃(CO)₁₀(m?₃-η²-C? C(H)OC₂H₅) 4 by 1,2 proton shift. The alkyne clusters Fe₃(CO)₁₀(m?₃-η²-C? C(H)OC₂H₅) 4 by 1,2 proton shift. The alkyne clusters Fe₃(CO)₁₀(m?₃-η²- H₃ C? O? CH₂? C?C? CH₂? O? CH₃) 6 and Fe₃(CO)₉(m?-η²-H₃C? O? CH₂? C?C? CH₂? O? CH₃) 7 are the isolated products obtained from 2c . Thermolysis of 7 results in the formation of the dinuclear butatrien complex Fe₂(CO)₆ (H₂C? C? C? CH₂) 8a . The analogous compound Fe₂(CO)₆[H(H₃C)C ? C ? C ? C(CH₃)H] 8b is the only product of 2d and 1 . The structures of 4, 5 , and 6 have been determined by crystal structure determinations.     

Reaktionen von Bortrihalogeniden mit Tris-(trimethylsily)-amin

Interaction of Borontrihalides and Tris-(trimethylsilyl)-amine According to the reaction conditions and the used halides borontrihalides BX₃ (X = F, Cl, Br) and tris-(trimethylsily1)-amine, (Me₃Si)₃N, I, (Me ? CH₃—) interact to give MeBX₂, (Me₃Si)₂N? BMeX, (Me₃Si)₂N? BX₂ or mixtures of these compounds; e. g. BF₃, and I yield (Me₃Si)₂N? BF₂ and Me₃SiF, while BBr₃ and I at 23°C form MeBBr₂ and (Me₃Si)₂NSiMe₂Br. In addition the unknown aminoboranes (Me₃Si)₂N? BMe₂ and (Me₃Si)₂N? BMeBr were synthesized using a different route.     

Analytische Reaktionen von N-Furoylphenylhydroxylamin (R) mit Metallen

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