Beiträge zur Chemie des Brompentafluorids. 4. Arylbrom(V)-dioxide und -fluoridoxide

Contributions to the Chemistry of Brominepentafluoride. 4. Arylbromine(V) Dioxides and Fluorideoxides . Arylbromine(V) tetrafluorides RBrF₄ (R=C₆F₅, p- and m-CF₃C₆H₄, o-FC₆H₄) react in aimed hydrolysis reactions or with (Me₃Si)₂O to the corresponding arylbrominedioxides RBrO₂. However with CsNO₃ as reagent for fluorine-oxygen substitution arylbrominedifluorideoxides RBrOF₂ are formed. Fluorine-oxygen substitution reactions on BrF₅ with (Me₃Si)₂O and [F₃CC(O)]₂O in organic solvents proceed via polysubstitution and end under formation of BrO₂F whereas with C₆F₅C(O)OSiMe₃ via monosubstitution BrOF₃ is obtained. In organic solvents bromine(V) fluorideoxides are — similar to BrF₅ — principally accessible to fluorine-aryl substitution what is demonstrated by the formation of C₆F₅BrO₂ from BrO₂F.     

Beiträge zur Chemie des Siliciums und Germaniums. XXXIII [1]. Zur Darstellung von Kaliumsilyl

Reines, monoglyme- und kaliumhydridfreies, kristallines Kaliumsilyl wird aus Monosilan und Na/K-Legierung in Monoglyme unter Anwendung einer speziellen Art der Dosierung von Monosilan erhalten. Die analytische Charakterisierung der Verbindung ist durch Hydrolyse sowie durch Umsetzung mit Benzylchlorid und nachfolgende gaschromatographische Untersuchung des Reaktionsproduktes möglich. Löslichkeitsuntersuchungen von Kaliumsilyl in verschiedenen Solventien haben in Monoglyme eine zunehmende Löslichkeit mit abnehmender Temperatur ergeben. Die Leitfähigkeit einer Lösung von Kaliumsilyl in Monoglyme ist gemessen worden. Contributions to the Chemistry of Silicon and Germanium. XXXIII. On the Preparation of Potassium Silyl Pure, crystalline potassium silyl, free of glyme and potassium hydride, is prepared from monosilane and Na/K alloy, using a special method of dosing the monosilane. The substance was characterized by hydrolysis and by gaschromatographic investigation of the products from its reaction with benzyl chloride. Studying the solubility of potassium silyl in different solvents an increasing solubility in glyme is observed while the temperature is lowered. The conductivity of a solution of potassium silyl in glyme has been measured.     

Beiträge zur Chemie des Arsens. 5. Zur Existenz von Penta-tert-butyl-cyclopentaarsan, (t-BuAs)5

Contributions to the Chemistry of Arsenic. 5. On the Existence of Penta-tert-butyl-cyclo-pentaarsane, (t-BuAs)₅ The reaction of tert-butyldichlorarsane with magnesium in tetrahydrofurane or diethylether yields the hitherto unknown penta-tert-butyl-cyclopentaarsane, (t-BuAs)₅ ( 1 ), in addition to the cycloarsanes (t-BuAs)₄ and t-Bu₆As₈. Compound 1 was preparatively concentrated to ? 80 mole-% and characterized by its ¹H-NMR and mass spectrum. The thermodynamic stability of the tert-butyl substituted monocyclic arsanes decreases in the order (t-BuAs)₄ > (t-BuAs)₅ > (t-BuAs)₃. By thermolysis of 1 t-Bu₆As₈ and other polycyclic arsanes are formed.     

Beiträge zur Chemie von Phosphorverbindungen mit Adamantanstruktur. X. Zur Solvolyse von Phosphor(III/V)-oxiden

Contributions to the Chemistry of Phosphorus Compounds with Adamantane Structure. X. Solvolysis of Phosphorus(III/V) Oxides The phosphorus(III/V) oxides of adamantan-like structure have been prepared by oxydation of phosphorus or of phosphorus trioxide with oxygen and characterized by analysis in water solution and by ³¹P n.m.r. spectroscopy. Paper chromatographic and n.m.r. studies show that the alcoholysis of the phosphorus(III/V) oxides leads to tri-, di-, and monoesters of phosphorous acid and also to mono-, di-, and cyclotriphosphoric acid, in dependence on their P^III and P^V contents. Nucleophilic attack by the alcohol takes place not statistically but in principle on the P^III atoms of the phosphorus(III/V) oxide molecule and their primary degradation products. In analogy to the alcoholysis the hydrolysis of the phosphorus(III/V) oxides yields phosphorous acid, mono-, di-, and cyclotriphosphoric acid. The mechanism of degradation is discussed.     

Beiträge zur Chemie des Bors. 207. Reaktionen von 1,3,2,4-Diphosphadiborabicyclo[1.1.0]butanen

Contributions to the Chemistry of Boron. 207. Reactions of 1,3,2, 4-Di-phosphadiborabicyclo[1.1.0]butanes The diphosphadiborabicyclobutanes 1 and 2 react with diiron enneacarbonyl or cymantrentricarbonyl, respectively, to the mono or dinuclear complexes 3–8 . The X-ray analysis of the manganese complex 7 shows the stability of the bicyclobutane framework with a P? P bond length nearly unchanged in comparision to the free ligand. Whereas BBr₃ reacts with 1 to form the adduct 9 , BH₃ · THF splits the B? P bonds with formation of tmpBH₂. The reaction of the bicyclus with sulfur also leads to its degradation — P₄S₁₀ and α-P₄S₄ are detected, the dithiadiboretane 12 is isolated. The P? P bond in 1 is split by lithium metal to mono or dilithium derivatives of the diphosphadiboretane 13 and 14 . The reaction of 13 with Et₂NBCl₂ leads to the borylsubstituted diphosphadiboretane 17 .     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. XLIX. Reaktionen von Cerium(IV)-acetylacetonat mit Lithium- und Magnesiumorganylen

Contributions to the Chemistry of Organo Transition Metal Compounds. XLIX. Reactions of Cerium(IV) Acetylacetonate with Organolithium and Organomagnesium Compounds Reacting Ce(acac)₄ with lithium organyls RLi (R = CH₃ 1-Nor¹), ((CH₃)₂NCH₂CH₂CH₂) in the molar ratio 1:1 the cerium compound is reduced with formation of Li[Ce(acac)₄]. Using a molar ratio of Ce:Li = 1:4 organocerium complexes of the composition R₃Ce · 3 Li(acac) or Li₃[R₃Ce(acac)₃] are formed. From reactions with excess CH₃Li (Ce: Li = 1:7) Li₃[Ce(CH₃)₆] · 3 Li(acac) could be isolated. All cerium complexes are characterized by elementary analysis, hydrolysis products, i.r. spectra, and molecular weight determination.     

Beiträge zur Chemie des Hydrazins und seiner Derivate. XIX. Über die Umsetzung von Bariumpernitrid,Ba3N4, mit Dimethylsulfoxid

The reaction of barium pernitride with dimethylsulphoxide yields via the methylsulphinylcarbanion an amorphous polymeric substance, which according to IR-spectroscopic studies possesses a thermally very stable structure, probably containing S? C? S units as basic elements. An attempt is made to interprete the mechanism of this polymerisation.     

Beiträge zur Chemie des Phosphors. 168 [1]. Zur Kenntnis der Isomere von Tetraphosphan(6), P4H6

Contributions to the Chemistry of Phosphorus. 168. About the Isomers of Tetraphosphane(6), P₄H₆ Additional informations about the ³¹P-NMR parameters of d,l- and meso-n-P₄H₆ as well as of iso-P₄H₆ have been obtained by ³¹P-NMR spectroscopic investigations of mixtures of phosphanes containing 26—48 P-% of tetraphosphane(6). On the basis of the differences in the ³J(PP)-coupling constants the observed AA′BB′-spin systems have been reassigned to the various diastereomers of n-P₄H₆.     

Beiträge zur Chemie des Siliciums und Germaniums. XXX [1]. Die photochemische Disproportionierung von iso- und n-Pentasilan. Darstellung einiger neuer verzweigter Hepta- und Octasilane

Contributions to the Chemistry of Silicon and Germanium. XXX. Photochemical Disproportionation of iso- and n-Pentasilane Preparation of Some New Hepta- and Octasilanes Solutions of iso- and n-pentasilane in 2,3-dimethylbutane were irradiated at room temperature by UV-light. The photolytic decomposition of the pentasilanes to higher and lower homologes was controlled by gas chromatography. The main reaction can always be described as disproportionation of the pentasilanes to trisilane and branched heptasilanes, or disilane and branched octasilanes. The new hepta- and octasilanes 3,3-disilylpentasilane and 2,3,3-trisilylpentasilane, obtained from iso-pentasilane, as well as 3-silylhexasilane and 4-silylheptasilane, obtained from n-pentasilane, were isolated and characterised by ¹H-NMR, Raman and mass spectrocsopy.     

Beiträge zur Chemie der Schwefelhalogenide. 14. Die Kinetik des Zerfalls von Diioddisulfan und Perfluormethyliodsulfan

Contribution to the Chemistry of Sulfur-Halogen Compounds. 14. Decomposition Kinetics of Diiododisulfane and Perfluoromethaneiodosulfane Due its bifunctional character, S₂I₂ decomposes by inter- as well as intramolecular iodine formation. A system of competing parallel and secondary reactions results. The main decomposition phase follows first order rate law and is strongly temperature dependent, on the other hand, perfluoromethaneiodosulfane decomposes obeying second order rate law, where K = 2.74 ± 0.03 × 10^?4 l mol^?1s^?1 at 40°C.     

Beiträge zur Chemie von Phosphorverbindungen mit Adamantanstruktur. XIV. Kristallstruktur eines 3, 5-Diphenyl-1, 2, 4-dithiazolium-Salzes mit käfigförmigem [P4NS9]-Anion

Contributions to the Chemistry of Phosphorus Compounds with Adamantane Structure. XIV. Crystal Structure of a 3, 5-Diphenyl-1, 2, 4-dithiazolium Salt with the Cage-like Anion [P₄NS₉] The compound 3, 5-Diphenyl-1, 2, 4-dithiazolium 1, 3, 5, 7-pentathioxo-10-aza-2, 4, 6, 8, 9-pentathia-1α⁵,3λ⁵,5λ⁵,7λ⁵-tetraphosphatricyclo[3.3.1.1^3,7]decanide has been prepared by the reaction of P₄S₁₀ with benzonitrile. It crystallizes in the triclinic space group P1 with a = 9.914 Å, b = 15.025 Å, c = 9.186 Å, α = 100.48°, β = 99.90°, γ = 90.66°, and Z = 2. The anion has the structure of a P₄S₁₀-like cage, in which one P? S? P group is replaced by the P? N? P group.     

Beiträge zur Chemie des Phosphors. 100 [1]. Pentamethyl-heptaphosphan(5), P7(CH3)5, und Pentamethyl-nonaphosphan(5), P9(CH3)5

Contributions to the chemistry of phosphorus. 100. Pentamethyl-heptaphosphane(5), P₇(CH₃)₅, and pentamethyl-nonaphosphane(5), P₉(CH₃)₅ Two new methylphosphanes with condensed ring systems, P₇(CH₃)₅ ( 1 ) and P₉(CH₃)₅ ( 2 ), have been obtained by reacting mixtures of phosphorus(III) chloride with methyldichlorophosphane or pentamethylcyclopentaphosphane in presence of magnesium. Besides, the formation of P₇(CH₃)₃, P₈(CH₃)₆ and P₁₁(CH₃)₅ has been detected. 1 and 2 can be isolated in a pure state and have been characterized by elemental analysis, mass, IR, and NMR spectra as compounds with a norbornane-analogous P₇-skeleton and a noradamantane-analogous P₉-skeleton, respectively. Thereby, at the same time the structures of the hydrides P₇H₅ and P₉H₅ have unambiguously been clarified as bicyclo[2.2.1]heptaphosphane and tricyclo[3.3.1.0^3,7]nonaphosphane, respectively. 1 and 2 are formed as mixtures of various configurational isomers which differ in the arrangement of the methyl groups.     

Beiträge zur Chemie und Struktur von Vanadylhalogeniden

Investigations on the Chemistry and Structure of Vanadyl-halogenides Aqueous solutions of VOI₂ can be prepared from VOSO₄ and BaI₂. By concentrating VOI · 3 H₂O is formed; but adducts of VOI₂ with DMSO and DMF can be isolated. The structure of [VO(DMSO)₅]I₂ was determined by X-ray single crystal techniques: Monoclinic; space group P2₁/c; a = 10.696; b = 10.877; c = 24.74 Å; ß = 109.87°; Z = 4. – Other new compounds are VO(OCH₃)Br · 3 pyr and VOBr₂ · 2 H₂O · 2 eth, which can be decomposed to VOBr₂. The structures of VOCl₂ and VOBr₂ were determined from crystal powders (space group I mmm). IR and reflection spectra (4–50 kK) and magnetic moments of all compounds were measured.     

Beiträge zur Chemie der Thiazylhalogenide. 9. Zur Chemie des Cyclopentathiazeniums S5N5+

Contributions to the Chemistry of Thiazylhalides. 9. On the Chemistry of the Cyclopentathiazenium, S₅N₅⁺ Preparation, properties, and reactions of a new thiazylchloride, S₅N₅⁺Cl^?, are reported. The chloride is a product of the direct reaction of S₄N₄ and (NSCl)₃. Using S₅N₅Cl, further new cyclopentathiazenium compounds (S₅N₅Br, S₅N₅Br₃, S₅N₅I₂Cl, and S₅N₅SbCl₄) could be prepared. Their properties show a strong dependence of the stability of the compound on the size of the anion present.     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. XXXVI. Zur Existenz von 3(N,N-Dimethylamino)propyl-Verbindungen der 3d-Elemente und des Zirconiums

Contributions to the Chemistry of Transition Metal Alkyl Compounds. XXXVI. About the Existence of 3(N, N-Dimethylamino)propyl Compounds of 3d-Metals and Zirconium 3(N, N-dimethylamino)propyl lithium reacts with 3d-metal halides in a different manner. In crystalline state the compounds RTiCl₃, R₃Cr, R₄Zr, and the complexes LiVR₃Cl · 0.7 O(C₂H₅)₂ and Li₂CoR₄ (R = (CH₃)₂NCH₂CH₂CH₂) were isolated. The formation of the unstable R₄Ti and R₂Ni derivatives could be proved. Iron and nickel halides are reduced to the metals by dimethylaminopropyl lithium, even at a temperature of ?60°C.     

Beiträge zur Chemie des Phosphors. 240 [1]. Zum reaktiven Verhalten von Diphosphan-boran,P2H4 · BH3

Contributions to the Chemistry of Phosphorus. 240. On the Reactive Behaviour of Diphosphane-borane, P₂H₄ · BH₃ Under mild temperature conditions, the thermal decomposition of diphosphane-borane ( 1 ) gives rise to the formation of phosphane-borane, PH₃ · BH₃, and triphosphane-2-borane, PH₂? PH(BH₃)? PH₂ ( 2 ). In the presence of diphosphane-1,2-bis(borane), triphosphane-1,3-bis(borane), BH₃? PH₂? PH? PH₂? BH₃ ( 3 ), is formed additionally. The thermolysis product at room temperature is a polymeric solid of varying composition which contains phosphorus, boron, and hydrogen. Compound 1 reacts with metalating agents such as n-BuLi, LiBH₄, and NaBH₄ to furnish the borane-trihydrogendiphosphide ion, [PH₂? PH? BH₃]^?, which immediately disproportionates to give the corresponding mono-and triphosphane derivatives. In the presence of an excess of THF-borane and in the case of a 1 : 1 molar ratio of 1 : NaBH₄, the disproportionation does not occur and the new diphosphide derivative sodium-1,1,2-tris(borane)-1,2,2-trihydrogendiphosphide, Na[(BH₃)₂PH? PH₂BH₃] ( 4 ) can be obtained. The action of additional NaBH₄ yields the diphosphide dianion with four coordinated BH₃ groups.     

Beiträge zur Chemie des Phosphors. 239 [1]. Reaktion von Diphosphan(4) mit Diboran(6) und mit THF-Boran: Bildung von Diphosphan-boran,P2H4 · BH3, und Diphosphan-1,2-bis(boran), BH3 · P2H4 · BH3

Contributions to the Chemistry of Phosphorus. 239. On the Reaction of Diphosphane(4) with Diborane(6) and with THF-Borane: Formation of Diphosphane-borane, P₂H₄ · BH₃, and Diphosphane-1,2-bis(borane), BH₃ · P₂H₄ · BH₃ Diphosphane(4) always reacts with diborane(6) in the temperature range of ?118 to ?78°C, to furnish a mixture of diphosphane-borane, P₂H₄ · BH₃ ( 1 ), and diphosphane-1,2-bis(borane), BH₃ · P₂H₄ · BH₃ ( 2 ), in addition to small amounts of triphosphane-1,3-bis(borane), BH₃ · P₃H₅ · BH₃, and phosphane-borane, BH₃ · PH₃, irrespective of the molar ratios of the reactants employed. The formation of the 1 : 1 adduct P₂H₄ · B₂H₆ reported in the literature [4] could not be confirmed. The structures of compounds 1 and 2 were investigated by nuclear magnetic resonance spectroscopy which revealed the complete, homolytic cleavage of diborane(6). As a result of the bonding of one BH₃ group to diphosphane(4), the Lewis basicity of the other PH₂ group is markedly reduced. Similar mixtures of products are obtained when the borane adduct THF · BH₃ is employed in an analogous reaction. In the case of a 1 : 1 molar ratio of P₂H₄ : THF · BH₃ at ?78°C, the reaction furnishes compound 1 exclusively. This product can be isolated in the pure state and is found to be appreciably more stable than diphosphane(4).     

Beiträge zur Chemie des Phosphors. 224. Zur Thermolyse von 1,2-Di-tert-butyldiphosphan, 1,2,3-Tri-tert-butyltriphosphan und Tetra-tert-butylcyclotetraphosphan

Contributions to the Chemistry of Phosphorus. 224. On the Thermolysis of 1,2-Di-tert-butyldiphosphane, 1,2,3-Tri-tert-butyltriphosphane, and Tetra-tert-butylcyclotetraphosphane On disproportionation of 1,2-di-tert-butyldiphosphane, H(t-Bu)P? P(t-Bu)H (1) , 1,2,3-tri-tert-butyltriphosphane, H₂(t-BuP)₃ (2) , is formed which reacts further at temperatures above 100°C to give 1-(tert-butylphosphino)-2,3,4-tri-tert-butylcyclotetraphosphan, P₅(t-Bu)₄H (4) . Compound 4 reacts with 1 or 2 with lengthening of the P-sidechain to furnish the corresponding 1-(1,2-di-tert-butyldiphosphino)-2,3,4-tri-tert-butylcyclotetraphosphane, P₆(t-Bu)₅H (5) . At temperatures above 170°C, 5 disproportionates into the tetra-tert-butylcyclotetraphosphane, (t-BuP)₄ (3) which is stable up to about 200°C, and the bicyclo[3.1.0]hexaphosphane P₆(t-Bu)₄ from which the polycyclophosphanes P₉(t-Bu)₃ and P₈(t-Bu)₆ arise during the further course of the thermolysis. These products are finally converted through even more phosphorus-rich and more highly condensed t-butylcyclophosphanes into elemental phosphorus. In each reaction step, varying amounts of the monophosphane derivatives t-BuPH₂, (t-Bu)₂PH, and (t-Bu)₃P are formed. The proposed course of the reaction is further substantiated by the pyrolysis products of pure 2 and 3 .     

Beiträge zur Chemie des Phosphors. XXXIX. Zur Hydrolyse des Diphosphor-tetrajodids

In the preparation of Ba₂H₂(H₂P₂O₄)₃ by P₂I₄ hydrolysis in barium acetate/acetic acid buffer solution P(II)—P(IV), P(IV)—P(IV), P(III), and P(V) acid are formed in addition to about 17% of the starting phosphorus as P(II)—P(II) acid after separating the Ba₂H₂(H₂P₂O₄)₃. Thus in this reaction a total of 64% of P₂I₄ Phosphorus can be detected as hypodiphosphorous acid H₄P₂O₄. The precipitated yellow reaction product, obtained by water hydrolysis of P₂I₄, contains no solid phosphorus hydride — as believed previously — but as a result of elementary analysis, iodometry, and chromatography, a high molecular-weight phosphorus, hydrogen and oxygen containing substance of statistical stoichiometry with oxydation number ～0 for phosphorus. P? H, P?O, and P? O? P groups could be detected by IR-spectroscopy, but not P? OH groups. The P₂I₄ hydrolysis probably proceeds via a yellow coloured initial product with trivalent phosphorus, and yields a very complex reaction mixture in which also the intermediates partially still react further.     

Beiträge zur Chemie des Phosphors. 181 [1, 2]. Dinatrium-hydrogenhenicosaphosphid Na2HP21

Contributions to the Chemistry of Phosphorus. 181. Dinatrium Hydrogen Henicosaphosphide Na₂HP₂₁ The hydrogen henicosaphosphide Na₂HP₂₁ ( 2 ) has been obtained as the final product in the reaction of trisodium henicosaphosphide, Na₃P₂₁ ( 1 ), with acetylacetone or glacial acetic acid. The attack of the proton occurs at the phosphide P atom of the P₇(5)? middle group analogous to norbornane, the site of greatest nucleophilicity of the P₂₁^3? ion. The basicity of the HP₂₁^2? ion toward the above-mentioned protonating agents is not sufficient for the formation of P₂₁H₃; a rearrangement of the P₂₁(3) skeleton takes place on reaction with stronger acids.