Über die Darstellung von Verbindungen des Typs Cl3VNR

The reaction of VOCl₃ with sily-substituted amines results in the substitution of oxygen in VOCl₃ and in compounds of type Cl₃V = NR. In this way, we succeeded in isolating the pure compound Cl₃V = NCH₃ (I). The existence of compound (Cl₃VNC₆H₅)_x (II) was proved by direct synthesis from Cl₃VO and ((CH₃)₃Si)₂NC₆H₅, and by the decomposition of the new addition compounds Cl₃VO · 2 OCNC₆H₅ (III) and Cl₃VO · 2 OSNC₆H₅ (IV).     

Determination of the thermodynamic excess functionsG E,H E,andS E of the liquid ternary system AgCl—LiCl—KCl by means of EMF-measurements

By means of EMF-measurements using the formation cell $$graphite/Ag/AgCl(l,x_{AgCl} ) - LiCl(l,x_{LiCl} ) - KCl x_{KCl} /(Cl_2 )graphite$$ the partial molar excessGibbs energies,G _AgCl ^E , of silver chloride in the ternary system AgCl?LiCl?KCl were determined over the whole concentration range at five temperatures between 973 K and 1,123 K. The experimentally determinedG _AgCl ^E -values were fitted using theRedlich-Kister equation. From theRedlich-Kister parameters and their temperature dependence, obtained by the fitting procedure, the integral and partial molar excessGibbs energies, heats of mixing, and excess entropies were calculated. The fitting process permits also the calculation of the thermodynamic excess function of the binary system lithium chloride—potassium chloride.     

Selective halogenation at the pnictogen atom in Lewis-acid/base-stabilised phosphanylboranes and arsanylboranes

The halogenation of Lewis-acid/base-stabilised phosphanylboranes () and arsanylboranes () with CX(4) (X = Cl, Br) leads selectively to the substitution of both protons at the pentel atom and the new compounds [(CO)(5)W(X(2)PBH(2).NMe(3))] (: X = Cl, : X = Br) and [(CO)(5)W(X(2)AsBH(2).NMe(3))] (: X = Cl, : X = Br), respectively, are obtained. The new products were comprehensively characterised by spectroscopic methods and by X-ray crystallography. While compounds and show an antiperiplanar arrangement of the Lewis acid (W(CO)(5)) and the Lewis base (NMe(3)) in the solid state, a synclinal arrangement in and , respectively, was observed. Computational calculations of the optimised antiperiplanar and synclinal geometries of the compounds and in the gas phase slightly favour the antiperiplanar arrangement of the Lewis acid and the Lewis base for both compounds.     

Übergangsmetall-methylen-komplexe: LVI. Organoruthenium-komplexe mit offenkettigen und carbocyclischen alkyliden-brücken: Synthese,konstitution, isomerie,protonierung und thermolytischer abbau

The eighteen new μ-alkylidene ruthenium complexes 5a–r and 5t are very easily and cleanly obtained along the diazoalkane or the hydrazone routes that involve treatment of the dinuclear, metal-metal doubly bonded precursor compound [(η⁵-C₅H₅)Ru(μ-NO)]₂ (3) either with the diazoalkanes oxidizing agent (e.g., MnO₂), with the respective hydrazones. Similarly, sulfur dioxide adds cleanly to the RuRu double bond of 3, thus giving the complex (μ-SO₂)[(η⁵-C₅H₅)Ru(NO)]₂ (5s). Regardless of the nature of the carbene bridge ligands, the dimetallacyclopropanes exhibit, in contrast to their iron analogues, exclusively terminal nitrosyl ligands. cis/trans-Isomerism with predominating amounts of the trans-isomers is observed for the derivatives that display unsymmetrically substituted carbene bridges.Treatment of the μ-methylene- and μ-ethylidene complexes (μ-CH₂)[(η⁵-C₅H₅)Ru(NO)]₂ (5a) and (μ-CHCH₃)[(η⁵-C tetrafluoroboric acid or trifluoromethanesulfonic acid in diethyl ether yields, at ambient temperature, quantitatively the ionic complexes 6a,b and 7a,b, respectively, which were shown by ¹H NMR spectroscopy to contain metal-metal bridging hydrogen functionalities. The reaction of hydrogen bromide with 5a under the same conditions gives the neutral bromo(methyl) complex 6d. This latter compound results from the isolable ionic intermediate of composition [(μ-CH₂)(μ-H){(η⁵C₅H₅)Ru(NO)}₂]⁺Br^? (6c), which reaction stems from the nucleophilicity of the halide ion present in 6c.     

Metallorganische Verbindungen des Kupfers XIII. Kupfer(I)-chlorid-Komplexe winkelgespannter Cycloheptine Synthesen und Röntgenstrukturanalysen

The strained cycloheptynes 2a, 2b and 2c react with copper(I) chloride to form the dinuclear complexes [CuCl(cycloheptyne)]₂ 3a, 3b and 3c respectively. X-ray diffraction studies on all three compounds 3 show an increase in strength of the copper-alkyne bond with increasing deformation of the alkyne moiety from the ideal 180°. Thus going from the least strained alkyne (2c) to the most strained one (2a), the Cu-C bond lengths in the corresponding complexes decrease from 197.5 pm (3c) to 194.9 pm (3a). The C≡C-C angles increase from 145.6° (3a) over 147.4° (3b) to 151.6° (3c).

Zusammenfassung

Die gespannten Cycloheptine 2a, 2b und 2c reagieren mit Kupfer(I)—chlorid unter Bildung der zweikernigen Komplexe [CuCl(cycloheptin)]₂ 3a, 3b und 3c. Röntgenstrukturanalysen von allen drei Verbindungen 3 zeigen, daβ die Stärke der Kupfer—Alkin-Bindung zunimmt je mehr das ganze Alkinsystem vom idealen 180°-Winkel abweicht. Geht man vom am wenigsten gespannten Alkin (2c) zum gespanntesten (2a), so nehmen die Cu-C-Bindungslängen in den entsprechenden Komplexen von 197.5 pm (3c) auf 194.9 pm (3a) ab. Die C≡C-C-Winkel werden von 145.6° (3a) über 147.4° (3b) nach 151.6° (3c) hin gröβer.