Reaktionen von Tetraphosphortrichalkogeniden mit Alkyliodiden

Reactions of Tetraphosphorus Trichalcogenides with Alkyl Iodides Reactions of alkyl iodides RI (R = CHI₂, CH₂I or tert-Butyl) with P₄E₃ (E = S or Se) under the influence of light resulted in cleavage of the basal P₃ ring. β-P₄E₃(I)R was formed initially, then it rearranged to the more stable α-P₄E₃(I)R structure. ³¹P NMR data of these products were measured and discussed, along with ⁷⁷Se data for α- and β-P₄⁷⁷SeSe₂(I)CHI₂. On reaction of P₄S₃ with tert-butyl iodide in CS₂ or with sec-butyl iodide or iso-propyl iodide in dioxane, the new type of compounds P₅S₂R was observed. In this a sulfur bridge of P₄S₃ is replaced by a P? R group. ³¹P-NMR data for these compounds are reported.     

Reaktionen von Silylphosphanen mit Schwefel

Reactions of Silylphosphines with Sulphur We report about reactions of Me₂P? SiMe₃ 2 , MeP(SiMe₃)₂ 3 , (Me₃Si)₃P 4 , P₂(SiMe₃)₄ 5 , and (Me₃Si)₃P₇ 1 with elemental sulphur. Without using a solvent 2 reacts very vigorously. The reactions with 3 and 4 show less reactivity which is even more reduced with 5 and 1 . With equivalent amounts of sulphur the reactions with 2 , 3 , 4 lead to compounds with highest content of sulphur. These compounds are Me₃SiS? P(S)Me₂ 9 from 2 , (Me₃SiS)₂P(S)Me 13 from 3 and (Me₃SiS)₃P(S) 16 from 4 . Besides, the by-products (Me₃Si)₂S 8 , P₂Me₄ 7 , and Me₂P(S)? P(S)Me₂ 11 can be obtained. The reactions of silylphosphines in a pentane solution run much slower so that the formation of intermediates can be observed. Reaction with 2 yields Me₃SiS? PMe₂ 6 and Me₂P(S)PMe₂ 10 , which lead to the final products in a further reaction with sulphur. From 3 (Me₃SiS)(Me₃Si)PMe 14 and (Me₃SiS)₂PMe 12 can be obtained which react with sulphur to (Me₃SiS)₂P(S)Me 13. 4 leads to the intermediates (Me₃SiS)(Me₃Si)₂P 18 , (Me₃SiS)₂(Me₃Si)P 17 , (Me₃SiS)₃P 15 yielding (Me₃SiS)₃P(S) 16 with excess sulphur. Depending on the molar ratio (P₂SiMe₃)₄ 5 reacts to (Me₃Si)₂P? P(SSiMe₃)(Sime₃), (Me₃SiS)(Me₃Si)P? P(SSiMe₃). (Diastereoisomer ratio 10:1), (Me₃SiS)₂P? P(SiMe₃)₂ and (Me₃SiS)₂P? P(SSiMe₃)(Sime₃). With the molar ratio 1:4 the reaction yields (Me₃SiS)₂P? P(SSiMe₃)₂ (main product), (Me₃SiS)₃P(S) and (Me₃SiS)₃P. All silylated silylphosphines tend to decompose under formation of (Me₃Si)₂S. (Me₃Si)₃P₇ reacts with sulphur at 20°C (15 h) under decomposition of the P₇-cage and formation of (Me₃SiS)₃P(S). The products of the reaction of 5 with sulphur in hexane solution (molar ratio more than 1:3) undergo readily further reactions at 60°C under cleavage of P? P bonds and splitting off (Me₃Si)₂S, leading to (Me₃SiS)₃P(S) and cage molecules like P₄S₃, P₄S₇, and P₄S₁₀ and P? S-polymers. (Me₃SiS)₃P(S) isi thermally unstable and decomposes to P₄S₁₀ and (Me₃Si)₂S. Sulphur-containing silylphosphines like (Me₃SiS)P(S)Me₂ react with HBr at ?78°C under formation of Me₃SiBr (quantitative cleavage of the Si? S bond) and Me₂P(S)SH, which reacts with HBr to produce H₂S and Me₂P(S)Br.     

Reaktionen von Antimonpentahalogeniden mit Trichlornitromethan

Reactions of Antimony Pentahalides with Trichloronitromethane By reactions of SbCl₅ and SbF₅, respectively, with Cl₃CNO₂ the NO[SbCl₆] and until now unknown NO[Sb₂F₁₀Cl] can be obtained; the thermal decomposition of the latter complex leads to NO[Sb₂F₁₁]. The complexes are characterized by their vibrational spectra.     

Reaktionen von tetracarbonylhydridovanadium-verbindungen mit isopren

Disubstituted tetracarbonylhydridovanadium compounds (HV(CO)₄L₂, L₂ = dppm, arphos) react with isoprene to give η³-dimethylallyl complexes of the type (η³-dimethylallyl)V(CO)₃L₂. The compounds have been characterized and the isomers having methyl groups in various positions of the allyl ligand identified by ¹H NMR spectroscopy.     

Reaktionen von Titanocen-dichlorid mit Cysteamin

Reactions of Titanocene Dichloride with Cysteamine Cp₂TiCl₂ (Cp = η⁵-C₅H₅) reacts with HSCH₂CH₂NH₂ (cysteamine) in boiling tetrahydrofuran to give [Cp₂Ti(Cl)SCH₂CH₂NH₃]Cl ( IV ). Even at a 1:1 reagents molar ratio, further reaction of IV takes place partially to give by cleavage of a Cp ligand the new polymer [CpTi(Cl)SCH₂CH₂NH]_n ( V ). With 4 equivalents of cysteamine, pure V is obtained as a violet-red, air-sensitive powder which is thermally stable up to 130°C. In (CD₃)₂SO solution, a single ¹H NMR singlet appears at δ = 6.20 ppm for the Cp protons of V . Impure V is also formed from Cp₂TiCl₂ with HSCH₂CH₂NH₂ or [HSCH₂CH₂NH₃]Cl in the presence of triethylamine as HCl acceptor, or with LiSCH₂CH₂NH₂.     

Reaktionen von carben-komplexen mit tetramethylcyanoguanidin

Tetramethylcyanoguanidine, NCNC(NMe₂)₂, reacts with pentacarbonyl-[methoxy(phenyl)carbene]chromium, (CO)₅Cr[C(Ph)OMe], via substitution of the carbene ligand to give pentacarbonyl(tetramethylcyanoguanidine)chromium. X-ray structure analysis shows that the CrNCN fragment is nearly linear in the crystal, and that the CNC angle is 122.9(1)°. In solution rapid syn-anti isomerization at the NC double bond occurs. The reaction of tetramethylcyanoguanidine with pentacarbonyl[acetoxy(phenyl)carbene]-chromium and -tungsten, (CO)₅M-[C(Ph)OCO(O)Me] (M = Cr, W), yields (CO)₅M[C(PHNC(NMe₂)₂], where the acetoxy group of the carbene ligand is exchanged for the NC(NMe₂)₂ group of the cyanoguanidine.     

Reaktionen von tBuPLi2 mit Carbodiimiden

Reaction of ^tBuPLi₂ with Carbodiimides The reaction of bis(cyclohexyl)carbodiimide with ^tBuPLi₂ in THF at 20 °C leads to the tetranuclear Li‐complex [Li₄(THF)₂{^tBuP([^cHexN]₂C)₂}₂] ( 1 ). No addition on the carbodiimide but a silyl transfer was observed under similar conditions during the treatment of bis(trimethylsilyl)carbodiimide with ^tBuPLi₂ to give the lithium salts ^tBuP(SiMe₃)Li and [Li(THF)(Me₃SiN‐C≡N)]_n ( 2 ). 1 was characterized by NMR, IR and RE spectroscopy, mass spectrometry and X‐ray analyses. Theoretical calculations were performed for 1 . According to the structural investigations 1 consists ofa central centrosymmetrical twelve‐membered Li₂N₄C₄P₂ ring adjacent by two six‐membered LiN₂C₂P rings. The peripheric Li⁺ cations posssess coordination number (cn) 3 buildt‐up by two N atoms and a THF ligand, while the two central Li⁺ cations possess only cn 2. However, the theoretical calculations have shown no relevant bonding Li···Li or Li···P interaction.     

Einige Reaktionen von Phenoxy-amino-silanen mit Alkaliamiden

Zusammenfassung Es werden einige weitere Austauschreaktionen von Phenoxygegen Aminogruppen am Si-Atom mit Hilfe von (substitutierten) Alkaliamiden beschrieben. Sie sind in den Gl. (1) bis (7) niedergelegt. Dabei wird nur eine Phenoyxygruppe pro Molekül ausgetauscht, selbst bei Anwesenheit mehrerer Phenoxysilylgruppen und Anwendung eines größeren Alkaliamidüberschusses.The substitution of phenoxy by amino groups by means of alkali amides according equations (1)–(7) was feasible. However, even with several phenoxysilyl groups per molecule and an excess of alkali amide it was not possible to replace more than one phenoxy group.72. Mitt.:U. Wannagat, P. Schmidt undM. Schulze, Angew. Chem.79, 409 (1967).Mit Auszügen aus der DissertationG. Schreiner, Techn. Hochschule Graz, 1965.     

Photochemische Reaktionen von Acridan mit Hilfe von CIDNP

Ohne Zusammenfassung     

Die Reaktionen von Borverbindungen mit Oxychinonen

Ohne Zusammenfassung     

Reaktionen von Tetrachloroaurat mit verschiedenen Aminen

Reactions of Tetrachloroaurate with Various Amines . Tetrachloroaurate reacts with aminoalcohols (L) in aqueous solution to give the complexes [Au^IL₂][Au^IIICl₄]. With t-butylamine the complex AuCl₃(t-BuNH₂) has been obtained, whereas from the reaction of Na[AuCl₄] with n-butylamine the imine gold(I) complex ClAu(NH?CH(CH₂)₂Me) has been isolated.