Pyridinderivate als Komplexbildner VIII Die Herstellung je eines neuen vier- und sechszähnigen Liganden

The synthesis of the new complexing agents tris-(2-pyridylmethyl)-amine and N,N,N′,N′-tetrakis-(2-pyridylmethyl)-ethylenediamine is described, and their protonation constants are given.     

Die tertiäranregung in der quantitativen röntgenfluoreszenzanalyse

The theory of tertiary excitation of characteristic X-rays is treated. A computer evaluation of the equations shows for the ternary system Cr-Fe-Ni a contribution of 3 per cent at maximum to Cr-K-radiation, which can be excited tertiary. Of course it is also excited secondary by Fe- and Ni-radiation, but this influence has been discussed in an earlier paper [1].     

Zur Spaltung tertiärer Phosphine. I

Triphenyl phosphine and α,ω-bis-diphenylphosphino-alkanes may be cleaved on two reaction paths. Whereas alkaline metals in various solvents split off one phenyl group, two such groups are eliminated by commutation with phosphorus trichloride at 280°C under pressure, resulting in the formation of alkane-bis-dichlorophosphines the reactions of which are described.     

Trialkylbismutine als Liganden in Carbonylkomplexen des Eisens und der VIa-Elemente

Trialkylbismutines as Ligands in Carbonyl Complexes of Iron and Group VIa Elements The complexes (CO)₄FeBiR₃ (R = Et, Pr, Bu) are synthesized by reaction of Fe₂(CO)₉ and the corresponding bismutines. Complexes of the type Bu₃BiM(CO)₅ (M = Cr, Mo, W) are formed by irradiation of the hexacarbonyls of group VIa elements in tetrahydrofuran and subsequent addition of Bu₃Bi. The novel compounds are obtained in 40—90% yield. They are stable in an inert atmosphere above 25°C. Their ¹H-n. m. r., i. r., and m. s. data are discussed.     

Über die Reaktion von Phosphorpentachlorid mit den BF3-Addukten sekundärer und tertiärer Amine

Reaction of F₃B · NH(CH₃)₂ with PCl₅ yields [(CH₃)₂NPCl₃][BCl₄] (I), which can also be obtained by reaction of [(CH₃)₂NBCl₂]₂ with PCl₅. In BF₃ · N(CH₃)₃ the fluorine atoms are exchanged with chlorine atoms, by PCl₅, ³¹P, ¹⁹F, and ¹¹B-NMR spectra of the reactions products are described and discussed.     

Zur Spaltung tertiärer Phosphine. II

Commutation of 1-phenylphospholane and 1-phenylphosphorin with phosphorus trichloride at 280°C yields 1-chlorophospholane, C₄H₈PCl, and 1-chlorphosphorin, C₅H₁₀PCl, respectively which may be oxidized by elemental sulphur or chlorine, and hydrolyzed in the presence of hydrogen peroxide to from tetramethylene- and pentamethylene-phosphinic acid. Reduction by means of LiAlH₄ gives the cyclic secondary phosphines 1-phospholane, C₄H₈PH, and 1-phosphorin, C₅H₁₀PH.     

Zur Chemie von Sulfiden und Seleniden primärer Phosphane — Die (1-Hydroxyalkyl)-organyl-phosphansulfide und -selenide,neue Verbindungsklassen

Investigation into Sulfides and Selenides of Primary Phosphines — The (1-Hydroxyalkyl)-organyl-phosphine Sulfides and Selenides, New Classes of Compounds Primary phosphines react with S₈ and Se₈, respectively, forming organylphosphine monosulfides, and monoselenides, respectively, RP(X)H₂ (X = S, Se) which are well characterized by ³¹P NMR spectroscopy. Organylphosphine monosulfides are detected in the reaction mixture of primary phosphines with 2,4-diaryl-1,3,2,4-dithiadiphosphetane-2,4-disulfides, too. The reaction of primary phosphines with sulfur or selenium proceeds in presence of most of the ketones without formation of any side product. The (1-hydroxyalkyl)-organyl-phosphine sulfides and selenides, respectively, RP(X)(H)C(OH)R¹R², are yielded generally in crystalline form. The X-ray crystal structure analysis of the (1-hydroxy-1-methyl-ethyl)-phenyl-phosphane sulfide (R = Ph, R¹ = R² = Me) has shown that in the crystal the molecules are chained via intermolecular O? H …? S hydrogen bridging bonds (O …? S = 328 pm). Aldehydes react with primary phosphines and sulfur forming bis(1-hydroxyalkyl)-phenyl-phosphine sulfides, RP(S)[CH(OH)R¹]₂. ¹H, ¹³C, and ³¹P NMR spectroscopic investigations allow to detect and to identify stereoisomers in some cases. Quantumchemical calculations reflect correctly which of the carbonyl compounds are able to react with the organylphosphine monosulfide formed as intermediate.