Neue Gemischtligandenkomplexe mit Perthiocarboxylaten

New Mixed Ligand Complexes with Perthio Carboxylates Solutions of O-methyl-1,1-dithiooxalate (i-dtoMe) and metal(II)-chlorides (Ni^II, Pd^II) in the molar ratio 2:1 react with equimolar amounts of homonuclear bischelates of other 1,1- and 1,2-dithio-compounds L (L = i-mnt, Etxan, dto) to mixed ligand complexes M(ptoMe)L with spontaneous convertion of the 1,1-dithiooxalate into the corresponding perthio ligand (ptoMe) by sulfur insertion. Tetraphenylphosphonium-(1,1-dicyanoethene-2,2-dithiolato)(O-methyl-1,1 -perthio-oxalato)niccolat(II), Ph₄P[Ni(i-mnt)(ptoMe)], crystallizes in the monoclinic space group P2₁/n with a = 11.019(2) Å, b = 13.648(3) Å, c = 20.882(3) Å, β = 92.565(7)°. The formation of the perthio ligand is confirmed by ¹³C-NMR.     

Neue colorimetrische Kaliumbestimmung mit Dipikrylamin

Zusammenfassung Es wird über die Weiterbildung eines vom Verfasser in den letzten Jahren entwickelten Verfahrens zur colorimetrischen Bestimmung von Kalium berichtet. Das Verfahren beruht auf der Messung der Restfärbung des im Überschuß angewendeten Fällungsmittels, nämlich des Magnesiumdipikrylaminats.     

Neue Tetrathiocyanato-diamin-Chromiate mit aliphatischen Monoaminen

New Tetrathiocyanato-diamine-chromiates with Aliphatic Monoamines Two new Reinecke salt like compounds were obtained by a substitution reaction of anhydrous K₃[Cr(NCS)₆] with aliphatic monoamines (n-propylamine and n-butylamine) in the molten state. The formulae of the [Cr(CNS)₄(n-propylamine)₂]^? and [Cr(NCS)₄(n-butylamine)₂]^? were proved by a series of double decomposition reactions with the hydrochlorides of heterocyclic N-bases and alkaloids and with cobalt(III)-amine bases, respectively. From spectroscopical investigations (u.v. and i.r.) some structural problems are resolved and discussed.     

Neue Rheniumkomplexe mit Trichalkogenido- und Tetrachalkogenido-Chelatliganden

New Rhenium Complexes Containing Trichalcogenido and Tetrachalcogenido Chelate Ligands The reactions of Cp*ReCl₄ with polychalcogenide salts such as Na₂S₄ or (NEt₄)₂Se₆ lead initially to the violet trichalcogenido chelate complexes Cp*ReCl₂(E₃) (E = S ( 3a ), Se ( 3b )) which, due to their functional chloro ligands, can be used as intermediates for further reactions. Upon hydrolysis in moist solvents or aminolysis with tert. butylamine 3a, b are converted into the tetrachalcogenido chelate complexes Cp*Re(O)(E₄) (E = S ( 4a ), Se ( 4b )) and Cp*Re(N^tBu)(E₄) (E = S ( 5a ), Se ( 5b )), respectively. X-Ray structure analyses were carried out for the three mononuclear cyclo-oligoselenido compounds 3b–5b . It appears that the size of the Se^2?_n chelate ring (n = 3 or 4) essentially depends on steric factors within the coordination sphere of rhenium.     

Neue Boride mit NbCoB2-Typ

NbNiB₂, TaNiB₂ and TaCoB₂ crystallize with NbCoB₂ type structure. The crystal structure of TaNiB₂ has been refined from powder diagrams (R=11.8%).     

Neue stellungsisomere Reineckesalzanaloga mit Meta- und Para-Toluylendiamin

New Position Isomeric Analoga of Reinecke Salt with m- and p-Tolylenediamine Two position isomeric Reinecke salt analogous complexes, [Cr(NCS)₄(m-TolyIenediamine)₂]^? and [Cr(NCS)₄(p-Tolylenediamine)₂]^?, were obtained by means of substitution reactions of anhydrous K₃[Cr(NCS)₆] with meta and para tolylenediamine, respectively, without solvent. The formulae of the new complex anions were established by preparation of 18 new derivatives with the hydrochlorides of some alksloides, and cobalt(III) amine bases. From electronic and IR spectral data some structural problems are solved. The thermal stability of some complexes was discussed on the basis of derivatographic analysis.     

Neue Additionsverbindungen von Germaniumtetrajodid mit organischen Basen

Four new stable addition compounds have been prepared by reaction of germanium tetraiodide with various tertiary amines. It is a case of adducts of 1:4 composition, in contrast to the 1:5 addition compound with triethylamine, which we have also prepared and investigated for comparison. Formation, properties, analytical results, conductometric measurements and spectral data (IR and¹H-NMR) of these adducts are described and discussed in terms of possible structural types and the nature of the bonding.

     

Neue rhodanilatähnliche Verbindungen mit Morpholin

Substitution reactions of K₃[Cr(NCS)₆] with morpholine were studied. The formula of the complex anion, [Cr(NCS)₄(morph)₂]^–, was established.23 new complex compounds of these types have been prepared from the hydrochlorides of some aliphatic or heterocyclic amines, alkaloids and cobalt(III)ammine bases resp.Their thermal behaviour and the mechanism of pyrolysis of these salts was studied by derivatographic methodes. From UV and IR spectra some structural problems are resolved and discussed.

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