Diphenyldichlorophosphonium trichloride-chlorine solvate 1:1, [PPh2Cl2]+Cl(3)(-).Cl2: an ionic form of diphenyltrichlorophosphorane. Crystal structures of [PPh2Cl2]+Cl(3)(-).Cl2 and [(PPh2Cl2)+]2[InCl5](2-)

An ionic form of diphenyltrichlorophosphorane, namely, diphenyldichlorophosphonium trichloride isolated as a dichlorine solvate (1), was obtained by treating PPh(2)Cl(3) with excess chlorine. The identity of this species was established by single-crystal X-ray analysis and (31)P, (1)H, and (35)Cl NMR and Raman spectra. Bis(diphenyldichlorophosphonium) pentachloroindate (2) was obtained by the reaction of diphenyltrichlorophosphorane with indium trichloride in dichloromethane for comparison purposes. Its identity was determined by (31)P NMR spectra and single-crystal X-ray analysis.     

Tetraarylester der μ-Imidodiphosphorsäure und ihre Thioderivate — Strukturuntersuchungen

Tetraarylesters of μ-Imido-Diphosphoric Acid and its Thio Derivatives — Structure Investigations New O,O′,O″,O?-tetratolyl- and ditolyl-diphenylesters of the μ-imido-diphosphoric acid and its mono and dithio derivatives were synthesized, compared with the corresponding tetraphenylesters and investigated by ¹H, ¹³C, and ³¹P NMR spectroscopy and X-ray crystal structure analysis. Structures of the O,O′,O″,O?-tetrakis-(2-methyl-phenyl)-μ-imidodiphosphate, 1b , as well as of the corresponding ortho-, meta- and para-tolylesters of the μ-imido-monothiodiphosphoric acid ( 2a , 2b , 2c ) were determined. All the compounds form dimers via N? H…?O hydrogen bonds in the crystal as well as in nonpolar solvents. The distances around the phosphorus atoms rise with decreasing electronegativity of the phosphorus substituents. Signs of the ²J_{P? N? P} coupling constants were determined by ¹³C{¹H, ³¹P} triple resonance experiments for some compounds. These constants become more negative owing to substitution of a phosphoryl by a thiophosphoryl group.     

Synthesis and Characterization of the New Copper Indium Phosphate Cu8In8P4O30

The system CuO/In₂O₃/P₂O₅ has been investigated using solid state reaction between CuO, In₂O₃ and (NH₄)₂HPO₄ in silica glass crucibles at 900 °C. The powder samples were characterized by X‐ray diffraction, thermal analysis and FT‐IR spectroscopy. Orange single crystals of the new quaternary phase were achieved by the process of crystallization with mineralizers in sealed silica glass ampoules. They were then analyzed with EDX and single‐crystal X‐ray analysis in which the composition Cu₈In₈P₄O₃₀ with the triclinic space group P$\bar{1}$ (No 2) with a = 7,2429(14) Å, b = 8,8002(18) Å, c = 10,069(2) Å, α = 103,62(3)°, β = 106,31(3)°, γ = 101,55(3)° and Z = 1 was found. The three‐dimensional framework consists of [InO₆] octahedra and distorted [CuO₆] octahedra, overcaped [InO₇] prisms and [PO₄] tetrahedra, also trigonal [(CuIn)O₅] bipyramids and distorted [(CuIn)O₆] octahedra, where copper and indium are partly exchanged against each other. Cu₈In₈P₄O₃₀ exhibits an incongruent melting point at 1023 °C.     

Vanadium(V) tartrato complexes: speciation in the H3O+(OH-)/H2VO4-/(2R,3R)-tartrate system and X-ray crystal structures of Na4[V4O8(rac-tart)2].12H2O and (NEt4)4[V4O8((R,R)-tart)2].6H2O (tart = C4H2O6(4-))

A study of the aqueous H3O+(OH-)/H2VO4-/(2R,3R)-tartrate system has been performed at 273 K in a 1.0 mol/L Na+(Cl-) ionic medium using 51V NMR spectroscopy. In this relatively complicated system, more than 12 different species were observed. Ligand concentration, vanadate concentration, and pH variation studies were carried out, particularly for the range of pH 5.8-8.0 and for pH 2.4. Chemical shifts, vanadium-ligand stoichiometry, and also composition and formation constants for some, but not all, species are given. Despite some reduction of vanadium(V) to vanadium(IV) in an acidic medium at pH approximately 2.4, the stoichiometries of the principal species in solution at this pH were determined. Electrospray ionization mass spectra for some solutions were obtained and were in accordance with the conclusions drawn from the speciation studies. A series of crystalline vanadium(V) tartrato complexes M4[V4O8(tart)2].aq were also prepared and characterized. X-ray diffraction studies of Na4[V4O8(rac-tart)2].12H2O (1) and (NEt4)4[V4O8((R,R)-tart)2].6H2O (2) revealed unique tetranuclear [V4O8(tart)2]4- ions for which the {V4O4} rings have boat conformations.     

Syntheses of Phosphoryl Chloro‐ and Bromofluorides and Crystal Structures of POFCl2 and POF2Cl

A simple procedure for the preparation of phosphoryl chlorofluorides, POFCl₂ and POF₂Cl, by chlorination of the appropriate potassium fluorophosphates, K₂PO₃F and KPO₂F₂, respectively, with PCl₅ is described. The analogous bromination with PBr₅ gives POFBr₂ and POF₂Br. However, due to low yields and high content of impurities, this method is not suitable for the synthesis of the former compound. Both chlorofluorides were crystallized from the melt at low temperatures and their crystal structures were determined by X‐ray diffraction at ?153 °C. Distorted tetrahedral molecules of POFCl₂ are only weakly associated through intermolecular O···Cl contacts forming infinite chains similarly as in crystalline POCl₃. In POF₂Cl, however, the chains are formed by the O···P contacts, and an additional P–O···Cl bridging leads to their linkage into a double‐chain structure.     

Phase Equilibria in the System CuO‐NiO‐P4O10 and Synthesis,Crystal Structure,and Characterization of the New Copper Nickel Oxide Phosphate Cu3NiO(PO4)2

The system CuO‐NiO‐P₄O₁₀ was investigated using a solid state reaction between CuO, NiO, and (NH₄)₂HPO₄ in quartz crucibles at 900 °C. The powder samples were characterized by X‐ray diffraction, TG/DTA, electrochemical measurements, IR, and UV/Vis spectroscopy. Single crystals of a new quaternary phase Cu₃NiO(PO₄)₂ were achieved by cooling the melted compound in a sealed, evacuated quartz ampoule. Cu₃NiO(PO₄)₂ crystallizes in the monoclinic space group P2₁/n (no 14) with a = 8.2288(2) Å, b = 9.8773(2) Å, c = 8.2777(3) Å, β = 107.82(2)°, Z = 4. The three‐dimensional framework consists of distorted tetragonal pyramides [Cu1O₅], distorted planar squares [Cu2O₄], octahedra [Cu3O₆], and [NiO₆] and [PO₄] tetrahedra. The TG‐DTA of the new phase showed an incongruent melting at 1055 °C. The open circuit voltage of this material was measured to determine the electrochemical properties. The measurement revealed an initial capacity of 236 Ah · g^–1 and a voltage plateau at 2.05 V. Furthermore, it was possible to identify the phase equilibria and to obtain the phase diagram at 900 °C.     

NEW POLYHETEROATOMIC CYCLIC MOLECULES CONTAINING ELEMENTS of the 13.–16. GROUP

During studies of the reactions of ─N(H)SiMe ₃ and ─N(Me)SiMe ₃ derivatives of Cl ₃ PNSO ₂ Cl with acetonitrile and BCl ₃ we have obtained six-membered polyheteroatomic cycles ?P(Cl ₂ )NSO ₂ (Cl)N(H) C(Me)N? and ?P(Cl ₂ )NS(O)(Cl)OB(Cl ₂ )N(Me)?.^{1, 2} In the system Ph ₂ PCl ₃ , H ₂ NSO ₂ Cl and HN(SiMe ₃ ) ₂ we have identified and isolated several P─N─S cycles, e.g. the reaction of Ph ₂ PCl ₃ with H ₂ NSO ₂ Cl gives Ph ₂ ClPNSO ₂ Cl³ which with HN(SiMe ₃ ) ₂ reacts to ?S(O ₂ )N(H)P(Ph) ₂ N(H)SO ₂ N(H)P(Ph) ₂ N(H)?, ?S(O ₂ )N(H)S(O ₂ )N(H)P(Ph) ₂ N(H)P(Ph) ₂ N(H)? and ?[S(O ₂ )N(H) P(Ph) ₂ NP(Ph) ₂ N(H)]⁺? Cl^?; Ph ₂ PCl ₃ with HN(SiMe ₃ ) ₂ gives N[P(Ph) ₂ N(H)SiMe ₃ ] ₂ ⁺ Cl^?, and H ₂ NSO ₂ Cl with HN(SiMe ₃ ) ₂ leads to SO ₂ (NHSiMe ₃ ) ₂ . The reaction of Ph ₂ PCl ₃ with HN(SiMe ₃ ) ₂ gives N(P(Ph) ₂ NHSiMe ₃ ) ₂ Cl in a very good yield which was further used to syntheses of metal-containing heterocycles. By the reaction of N[P(Ph) ₂ N(H)SiMe ₃ ] ₂ ⁺Cl^? with some covalent halogenides we have obtained six-membered heterocycles containing B, As, In, and Sn. The same cyclic compounds can also obtained by the reaction of N[P(Ph ₂ )NH ₂ ] ₂ ⁺Cl^? or HN(P(R ₂ )N(H)SiMe ₃ ) ₂ with covalent halogenides.^4?6 However, the synthetic route via N[P(Ph) ₂ NHSiMe ₃ ] ₂ ⁺Cl^? is more convenient and gives the compounds in almost quantitative yields. The identity of all compounds was unambiguously establised by their X-ray structure determination.     

The polysulfonylamines bis(methylsulfonamido) sulfone and bis(trifluoromethylsulfonamido) sulfone

Bis­(methyl­sulfon­amido) sulfone, C₂H₈N₂O₆S₃ or SO₂(NHSO₂CH₃)₂, was synthesized from imidobis­(sulfonyl ­chloride), HN(SO₂Cl)₂, and bis­(tri­methyl­silyl)­methane, CH₂[Si(CH₃)₃]₂, in ­chlorotri­methyl­silane solution. In the solid state, there are two independent mol­ecules linked by two N—H⋯O hydrogen bridges into infinite chains parallel to the b axis. The central S atoms of the independent molecules each lie on a twofold axis. Bis­(tri­fluoro­methyl­sulf­onamido) sulfone, C₂H₂F₆N₂O₆S₃ or SO₂(NHSO₂CF₃)₂, was formed by the reaction of tri­chloro­phosphazosulfuryl tri­fluoro­methane, Cl₃PNSO₂CF₃, with fluoro­sulfonic acid, FSO₃H. The mol­ecules are connected by bifurcated N—H⋯O bridges into infinite layers parallel to the [001] plane. The central S atom lies on a twofold axis.