Synthese und Reaktivität von Silicium-übergangsmetall-Komplexen: XXI. Ferrio-azidosilane and Ferriosilyl-iminophosphorane

Reaction of the ferriochlorosilanes R₅C₅(CO)₂FeSiR′_3-nCl_n (1a–1f) with sodium azide in tetrahydrofuran yields the ferrio- (mono-, bis-, and tris-azido)silanes R₅C₅(CO)₂FeSiR′_3-n(N₃)_n (R = H, Me; R′ = Me, H; n = 1–3) (2a–2f). CCl₄ converts Cp(CO)₂FeSiMe(H)N₃ (2a) into the ferrioazido(chloro)silane Cp(CO)₂-FeSiMe(Cl)N₃ (3). Treatment of 2d, 2f with Me₃P results in the formation of the ferriosilyl-iminophosphoranes Cp(CO)₂FeSi(N₃)(R)NPMe₃ (R = Me, N₃), (4a, 4b) by N₂ elimination.     

Synthese und Reactivität von (2,6-iPr2Ph-dad)Ni(C2F4)

Upon warming the reaction mixture of Ni(cdt), C₂F₄, and 2,6-ⁱPr₂Ph-dad in THF from −78°C to room temperature the red-violet complex (2,6-ⁱPr₂Ph-dad)Ni(C₂F₄) (1) is obtained. 1 reacts with ethene already at −78°C by coupling of the olefinic ligands with the nickel atom to form the blue nickelatetrafluoro-cyclopentane compound (2,6-ⁱPr₂Ph-dad)Ni(C₂H₄C₂F₄) (2).     

Synthese und eigenschaften von trifluormethyl-Molybdän- und -Wolfram-Verbindungen

Under polar conditions Cd(CF₃)₂ complexes react with (CO)₃CpMCl ( M = Mo, W) to form the corresponding M-CF₃ compounds. (CO)₃CpMoCF₃ is identified by comparing its spectroscopical data with the described ones. The ¹H-, ¹³C, ¹³C, ¹⁹F-, and ¹⁸³W-NMR spectra, the i.r. and mass spectra of the new compound (CO)₃CpWCF₃ are discussed. Both M-CF₃ compounds do not react as polar trifluoromethylation reagents.     

Synthese und reaktivität von dienylmetall-verbindungen XXVIII. Über kationen des typs [C5H5Fe(CO)L(EME2)]+ (E = S,Se, Te)

The chiral cations, [CpFe(CO)(EMe₂)L]⁺, are obtained both by reaction of [CpFe(CO)(EMe₂)₂]⁺ with the ligands (L) by heating, and by irradiation of the cations [C₅H₅Fe(CO)₂EMe₂]⁺ in the presence of L (E = S, Se, Te; L = PR₃, AsR₃, SbR₃). The inversion about the chalcogen atom is investigated by DNMR spectrocopy. Compounds of the type [C₅H₅Fe(TeMe₂)L₂]⁺] are formed by irradiation of [C₅H₅Fe(CO)₂(TeMe₂)]⁺ and the ligands (L₂ = 2 PR₃, R = CH₃, OCH₃, OC₆H₅; L₂ = R₂P(CH₂)_nPR₂, R = C₆H₅, n = 1,2,3). ⁷⁷Se and ¹²⁵Te NMR data vary according to the donor properties of the ligand L in the complexes.     

Synthese,Struktur und Reaktivität von funktionalisierten Stibanidokomplexen des Eisens und Rutheniums [(η5-C5Me5)(CO)2MSbR1R2] (M = Fe,Ru; R1, R2 = SiMe3, C(O)tBu,C(O)Ph,C(O)-1 Ad)

Synthesis, Structure, and Reactivity of Functionalized Stibanido Complexes of Iron and Ruthenium [(η⁵-C₅Me₅)(CO)₂MSbR¹R²] (M = Fe, Ru; R¹, R² = SiMe₃, C(O) t Bu, C(O)Ph, C(O)-1 Ad) The reaction of equimolar amounts of [(η⁵-C₅Me₅)(CO)₂RuSb(SiMe₃)₂] ( 1 b ) and the carboxylic chlorides RC(O)Cl (R = tBu, Ph, 1-adamantyl) afforded the acyl(trimethylsilyl)stibanido complexes [(η⁵-C₅Me₅)(CO)₂RuSb · {C(O)R}(SiMe₃)] 2 b (R = tBu), 4 b (R = Ph), and 6 b (R = 1-Ad). The treatment of 1 b with two molar equivalents of pivaloyl chloride and benzoyl chloride led to the diacylstibanido complexes [(η⁵-C₅Me₅)(CO)₂RuSb{C(O)R}₂] ( 3 b , 5 b ). Analogously, the iron complex [(η⁵-C₅Me₅)(CO)₂FeSb · (SiMe₃)₂] ( 1 a ) is converted into the corresponding diacylstibanido complexes 3 a (R = tBu), 5 a (R = Ph) and 7 a (R = 1-Ad) by an excess of acid chloride. The treatment of 1 a with equimolar amounts of RC(O)Cl gave inseparable mixtures of starting material and the monoacyl- and diacyl stibanido complexes. Oxalyl chloride reacted quantitatively with two equivalents of 1 a to give complex [{(η⁵-C₅Me₅) · (CO)₂FeSb(SiMe₃)C(O)}₂] ( 8 ). The molecular structures of 1 a , 2 b and 5 b were elucidated by single crystal X-ray analyses.     

Synthese und reaktivität ternärer cluster: Photochemisch ausgelöste insertion von alkinen in (μ3-RP)Fe3(CO)10

The RP bridged clusters (μ₃-RP)Fe₃(CO)₁₀ (1) react with diphenylacetylene upon irradiation to yield three different isomers (RP)(PhCCPh)Fe₃(CO)₉ (2–4) depending on the reaction conditions. X-ray diffraction analysis of the isomers shows that in 2, which appears to be the primary photochemically formed product, the alkyne is inserted between a phosphorus and an iron center of 1. For isomer 3 one of the PFe bonds of the starting cluster 1 is bridged by the alkyne while in 4 the alkyne is inserted into an FeFe edge of 1. These observations suggest that photochemical activation of 1 involves homolytic PFe bond scission with consequent decarbonylation.     

Copolymerisation von Itaconsäuréanhydrid und Styroi,Bestimmung der Reaktivitätsverhältnisse

Ohne Zusammenfassung     

Synthese und Geruch von (Z)-Dehydro-homo-β-santalol

Summary Guided by molecular modeling studies, the synthesis of the title compound is described. The organoleptic evaluation proved the predicted real sandal like odour of (Z)-dehydro-homo--santalol.

Aus den Diplomarbeiten von C.P. (1991), I.P. und B.Ö. (1992), Universität Wien     

Synthese und Reaktionen von Ferrocenoyl-acetaldehyd und Ferrocenyl-(β-chlorvinyl)-keton

Zusammenfassung Kondensation von Acetylferrocen mit Äthylformiat liefert Ferrocenoyl-acetaldehyd (I), der zum Ferrocenyl-(-chlorvinyl)-keton (II) chloriert werden kann. Die Reaktionsfreudigkeit beider Verbindungen konnte zur Darstellung neuer Ferrocenderivate ausgenützt werden: Davon seien die Umsetzungen mit Alkoholen (Fc-Ketoacetale), mit Hydrazin (Fc-Pyrazol) oder Harnstoff (Fc-Pyrimidon), die Dehydrochlorierung von II (Fc-äthinyl-keton) und die Trimerisierung von I genannt, die zum sym. Tris-ferrocenoyl-benzol führt. Über die Ketoacetale ist -Ferrocenylnaphthalin zugänglich, das — ebenso wie das -Isomere — auch durch Umsetzung von Ferrocen mit diazot. Naphthylamin erhalten werden kann.Auch Diacetylferrocen läßt sich zu einer Bis-(-dicarbonyl)-verbindung (XIII) kondensieren, die mit Hydrazin 1,1-Bispyrazolyl-ferrocen liefert.16. Mitt.:K. Schlögl undM. Fried, Mh. Chem.94, 537 (1963).     

Zur herstellung und reaktivität von bis(trimethylsilyl)dilithiomethan

At −90°C in THF or similar media bis(trimethylsilyl)dichloromethane 2 reacts with lithium-4,4′-di-tert-butylbiphenyl (LiDBB) or suspensions of freshly sublimed lithium to give the title compound 1 that can bind two equivalents of various electrophiles. 1 has a great propensity for proton abstraction and it is markedly less reactive towards ethyl iodide than (Me₃Si)2EtCLi6.     

Synthese von α-trifluormethyl-substituierten asparaginäuren und ihren devivaten

Syntheses of α-trifluoromethyl aspartic acid, β-substituted, and β,β-disubstituted α-trifluoromethyl aspartic acids are described.