On precipitation effects of aluminum,lanthanum, iron (III), and thorium phosphates

Summary Typical precipitation curves of various metal phosphates have been obtained using the turbidimetric technique. The following systems have been investigated: Al(NO₃)₃-K₃PO₄, Al(NO₃)₃-KH₂PO₄, Al(NO₃)₃NaH₂PO₄, FeCl₃-K₃PO₄, FeCl₃-(NH₄)₂HPO₄, FeCl₃K₂HPO₄, FeCl₃-KH₂PO₄, FeCl₃-NaH₂PO₄, La(NO₃)₃K₃PO₄,La(NO₃)₃-K₂HPO₄,La(NO₃)₃-KH₂PO₄,La(NO₃)₃NaH₂PO₄ and Th(NO₃)₄-K₂HPO₄. Typical precipitation curves indicated concentration ranges of phosphate precipitation and of complex solubility.

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Zusammenfassung Typische F?llungskurven verschiedener Metallphosphate, die mittels Trübungsmessungen erhalten wurden, wurden graphisch dargestellt. Die folgenden Systeme wurden untersucht: Al(NO₃)₃-K₃PO₄,Al(NO₃)₃KH₂PO₄, Al(NO₃)₃-NaH₂PO₄, FeCl₃-K₃PO₄, FeCl₃(NH₄)₂HPO₄, FeCl₃-K₂HPO₄, FeCl₃-KH₂PO₄, FeCl₃NaH₂PO₄, La(NO₃)₃-K₃PO₄, La(NO₃)₃-K₂HPO₄, La(NO₃)₃-KH₂PO₄, La(NO₃)₃-NaH₂PO₄ und Th(NO₃)₄K₂HPO₄. Typische F?llungskurven zeigten Konzentrationsgebiete, in welchen die Metallphosphate gef?llt werden, sowie Konzentrationen, die zur Komplexbildung führten.

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Supported in part by the U.S. Army Research Office, Contract No. DA-ORD-10.     

Kryometrische Untersuchungen. IV. Lösungen von oxidischen Mo6+- und Cr6+-Verbindungen in geschmolzenem K2Cr2O7 und KNO3

The depression of freezing point of molten K₂Cr₂O₇ and KNO₃ as solvents was measured after addition of small concentrations of the following compounds: to K₂Cr₂O₇: MoO₃, CrO₃, (NH₄)₂CrO₄, K₂MoO₄, Na₂MoO₄, Li₂MoO₄, and Na₂Mo₂O₇, respectively; to KNO₃: CrO₃, (NH₄)₂Cr₂O₇ K₂Cr₂O₇, K₂CrO₄ and MoO₃, (NH₄)₆(Mo₇O₂₄) · 4 H₂O, K₂Mo₂O₇, K₂MoO₄, Na₂MoO₄ and Li₂MoO₄, respectively. It could be concluded from the measured values of the freezing point depression if a reaction between solvent and solute took place.     

The chemistry of chromyl fluoride III. Reactions with inorganic systems

Reactions of CrO₂F₂ with MF or MF₂ gave the corresponding M₂CrO₂F₄ and MCrO₂F₄ fluorochromates. With the Lewis Acids (SO₃, TaF₅, SbF₅) and (CF₃CO)₂O known and new chromyl compounds [CrO₂(CF₃COO)₂, CrO₂(SO₃F)₂, CrO₂FTaF₆, CrO₂FSbF₆, CrO₂FSb₂F₁₁] were produced. Chromyl fluoride and inorganic salts (CF₃COONa and NaNO₃) produced the following complexes - Na₂CrO₂F₂(CF₃COO)₂ and Na₂CrO₂F₂(NO₃)₂. Unusual solid products were obtained with CrO₂F₂ and NO, NO₂, SO₂.A new method of preparing CrO₂F₂ is also presented.     

Chemie polyfunktioneller liganden LXIII. Adamantankäfigverbindungen mit den heteroelementen arsen,stickstoff und silizium

The reaction of 1,1,1-tris(diiodarsinomethyl)ethane, CH₃C(CH₂AsI₂)₃ (I), with i-C₃H₇NH₂, n-C₄H₉NH₂, C₆H₅NH₂, p-CH₃C₆H₄NH₂ and [(CH₃)₃Si]₂NH in the presence of (C₂H₅)₃N as auxiliary base in THF gives the adamantane cage compounds CH₃C(CH₂AsNC₃H₇)₃ (III), CH₃C(CH₂AsNC₄H₉)₃ (IV), CH₃C(CH₂AsNC₆H₅)₃ (V), CH₃C(CH₂AsNC₆H₄CH₃)₃ (VI) and CH₃C[CH₂AsNSi(CH₃)₃]₃ (VII). VII is also obtained in the reaction of I with NaN[Si(CH₃)₃]₂. The by-product (CH₃)₃SiO(CH₂)₄I (VIII) could be isolated in both syntheses of VII. All compounds have been characterized by mass spectrometry and infrared, Raman and ¹H NMR spectroscopy.     

Pseudohalogenometallverbindungen: LVIII. Reaktionen von diphenylphosphorylazid und perfluor-n-hexylsulfonylazid mit triphenylphosphan-komplexen von platin(0), rhodium(I), iridium(I), ruthenium(0), kobalt(II) und kupfer(I)

Diphenylphosphorylazide N₃P(O)(OPh)₂ reacts with Pt(PPh₃)₃, Pt(PPh₃)₂(C₂H₄), trans-RhCl(CO)(PPh₃)₂, Ru(CO)₃(PPh₃)₂, CoCl₂(PPh₃)₂ and CuCl(PPh₃)₂ to give the azido complexes Pt(PPh₃)₂(N₃)R, Pt(PPh₃)₂(N₃)₂R₂, the urylene complex RhCl(PPh₃)₂(RNCONR) and the phosphine imine complexes Ru(CO)₃(RPPh₃)₂, CoCl₂(RNPPh₃)₂, CuCl(RNPPh₃)₂, respectively, (RP(O)(OPh)₂). The oxidative addition of n-C₆F₁₃SO₂N₃ to Pt(PPh₃)₄ and Pt(PPh₃)₂(C₂H₄) affords the complexes Pt(PPh₃)₂(N₃)R and Pt(PPh₃)₂(N₃)₂R₂, respectively, (RSO₂C₆F₁₃. The compounds are characterized by elemental analysis and by their IR spectra.     

The synthesis and structure of triphenylsiloxycyclotriphosphazenes

The triphenylsiloxy-substituted cyclotriphosphazenes, N₃P₃Cl₅OSiPh₃, gem-N₃P₃Cl₄(OSiPh₃)₂, N₃P₃(OSiPh₃)₆, and N₃P₃(OPh)₅OSiPh₃, have been prepared. The synthesis of gem-N₃P₃Cl₄(OSiPh₃)₂ involves the reaction of (NPCl₂)₃ with Ph₃SiONa to form the intermediates gem-N₃P₃Cl₄(OSiPh₃)₂(ONa) and gem-N₃P₃Cl₄(ONa)₂, which yield gem-N₃P₃Cl₄(OSiPh₃)₂ when treated with Ph₃SiCl. The compounds N₃P₃Cl₅OSiPh₃ and N₃P₃(OSiPh₃)₀ are formed by the condensation reactions of N₃P₃Cl₅OBuⁿ and N₃P₃(OBuⁿ)₆, respectively, with Ph₃SiCl. The compound N₃P₃(OPh)₅OSiPh₃ is synthesized by the reaction between N₃P₃(OPh)₅Cl and Et₃SiONa to first give the intermediate N₃P₃(OPh)₅ONa, which yields N₃P₃(OPh)₅OSiPh₃ when reacted with Ph₃SiCl. The structural characterization and properties of these compounds are discussed. The crystal and molecular structure of gem-N₃P₃Cl₄(OSiPh₃)₂ has been investigated by single-crystal X-ray diffraction techniques. The crystals are monoclinic with the space group P2₁/c with a = 16.850(8), b = 12.829(4), c = 18.505(15) Å, and β = 101.00(6)° with V = 3927 ų and Z = 4. © 1996 John Wiley & Sons, Inc.     

Phase diagrams of binary systems of alkylammonium tetrachlorometallates(II)

The phase diagrams of four binary systems (C₁₀H₂₁NH₃)₂CoCl₄?(C₁₆H₃₃NH₃)₂CoCl₄, (C₁₂H₂₅NH₃)₂CoCl₄?(C₁₆H₃₃NH₃)₂CoCl₄, (C₁₀H₂₁NH₃)₂ZnCl₄?(C₁₆H₃₃NH₃)₂ZnCl₄ and (C₁₂H₂₅NH₃)₂ZnCl₄?(C₁₆H₃₃NH₃)₂ZnCl₄ were investigated by means of DSC. These six compounds and their binary mixtures can retain energies between 74 and 115 J/g during solid-state transformations at temperatures between 70 and 105°C, and they are therefore being considered for potential use in solar energy systems.     

Synthesis,spectroscopic and structural characterisation of vanadium(IV) and oxovanadium(IV) complexes with arsenic donor ligands

The reaction of o-C₆H₄(AsMe₂)₂ with VCl₄ in anhydrous CCl₄ produces orange eight-coordinate [VCl₄{o-C₆H₄(AsMe₂)₂}₂], whilst in CH₂Cl₂ the product is the brown, six-coordinate [VCl₄{o-C₆H₄(AsMe₂)₂}]. In dilute CH₂Cl₂ solution slow decomposition occurs to form the V^III complex [V₂Cl₆{o-C₆H₄(AsMe₂)₂}₂]. Six-coordination is also found in [VCl₄{MeC(CH₂AsMe₂)₃}] and [VCl₄{Et₃As)₂]. Hydrolysis of these complexes occurs readily to form vanadyl (VO²⁺) species, pure samples of which are obtained by reaction of [VOCl₂(thf)₂(H₂O)] with the arsines to form green [VOCl₂{o-C₆H₄(AsMe₂)₂}], [VOCl₂{MeC(CH₂AsMe₂)₃}(H₂O)] and [VOCl₂(Et₃As)₂]. Green [VOCl₂(o-C₆H₄(PMe₂)₂}] is formed from [VOCl₂(thf)₂(H₂O)] and the ligand. The [VOCl₂{o-C₆H₄(PMe₂)₂}] decomposes in thf solution open to air to form the diphosphine dioxide complex [VO{o-C₆H₄(P(O)Me₂)₂}₂(H₂O)]Cl₂, but in contrast, the products formed from similar treatment of [VCl₄{o-C₆H₄(AsMe₂)₂}_x] or [VOCl₂{o-C₆H₄(AsMe₂)₂}] contain the novel arsenic(V) cation [o-C₆H₄(AsMe₂Cl)(μ-O)(AsMe₂)]⁺. X-ray crystal structures are reported for [V₂Cl₆{o-C₆H₄(AsMe₂)₂}₂], [VO(H₂O){o-C₆H₄(P(O)Me₂)₂}₂]Cl₂, [o-C₆H₄(AsMe₂Cl)(μ-O)(AsMe₂)]Cl·[VO(H₂O)₃Cl₂] and powder neutron diffraction data for [VCl₄{o-C₆H₄(AsMe₂)₂}₂].     

Thermal and X-ray diffraction analysis studies during the decomposition of ammonium uranyl nitrate

Two types of ammonium uranyl nitrate (NH₄)₂UO₂(NO₃)₄·2H₂O and NH₄UO₂(NO₃)₃, were thermally decomposed and reduced in a TG-DTA unit in nitrogen, air, and hydrogen atmospheres. Various intermediate phases produced by the thermal decomposition and reduction process were investigated by an X-ray diffraction analysis and a TG/DTA analysis. Both (NH₄)₂UO₂(NO₃)₄·2H₂O and NH₄UO₂(NO₃)₃ decomposed to amorphous UO₃ regardless of the atmosphere used. The amorphous UO₃ from (NH₄)₂UO₂(NO₃)₄·2H₂O was crystallized to γ-UO₃ regardless of the atmosphere used without a change in weight. The amorphous UO₃ obtained from decomposition of NH₄UO₂(NO₃)₃ was crystallized to α-UO₃ under a nitrogen and air atmosphere, and to β-UO₃ under a hydrogen atmosphere without a change in weight. Under each atmosphere, the reaction paths of (NH₄)₂UO₂(NO₃)₄·2H₂O and NH₄UO₂(NO₃)₃ were as follows: under a nitrogen atmosphere: (NH₄)₂UO₂(NO₃)₄·2H₂O → (NH₄)₂UO₂(NO₃)₄·H₂O → (NH₄)₂UO₂(NO₃)₄ → NH₄UO₂(NO₃)₃ → A-UO₃ → γ-UO₃ → U₃O₈, NH₄UO₂(NO₃)₃ → A-UO₃ → α-UO₃ → U₃O₈; under an air atmosphere: (NH₄)₂UO₂(NO₃)₄·2H₂O → (NH₄)₂UO₂(NO₃)₄·H₂O → (NH₄)₂UO₂(NO₃)₄ → NH₄UO₂(NO₃)₃ → A-UO₃ → γ-UO₃ → U₃O₈, NH₄UO₂(NO₃)₃ → A-UO₃ → α-UO₃ → U₃O₈; and under a hydrogen atmosphere: (NH₄)₂UO₂(NO₃)₄·2H₂O → (NH₄)₂UO₂(NO₃)₄·H₂O → (NH₄)₂UO₂(NO₃)₄ → NH₄UO₂(NO₃)₃ → A-UO₃ → γ-UO₃ → α-U₃O₈ → UO₂, NH₄ UO₂(NO₃)₃ → A-UO₃ → β-UO₃ → α-U₃O₈ → UO₂.     

Zur Bildung von Disilylphosphino-Element-Verbindungen des C,Si, P

The Formation of Disilylphosphino-Element Compounds of C, Si, P The reactions of (me₃Si)₂PLi · OR₂ a (OR₂ = 1 monoglyme or 2 THF; me = CH₃) with CH₃Cl, CH₂Cl₂, ClCH₂CH₂Cl and ClCH₂? C₆H₅ give the compounds (me₃Si)₂Pme, (me₃Si)₂P? CH₂? P(Sime₃)₂, (me₃Si)₂P? CH₂CH₂Cl, (me₃Si)₂P? CH₂CH₂? P(Sime₃)₂ and (me₃Si)₂P? CH₂C₆H₅ respectively. In the same manner a reacts with me₂SiCl₂ in a molar ratio 1:1 to (me₃Si)₂P? Sime₂Cl and in a molar ratio 2:1 to (me₃Si)₂P? Sime₂? P(Sime₃)₂ b . The compound b decomposes to [me₃SiP? Sime₂]₂ and (me₃Si)₃P at 220°C. In the reactions of a with ClP(C₆H₅)₂ and ClPme₂ the compounds (me₃Si)₂P? P(C₆H₅)₂ and (me₃Si)₂P? Pme₂, respectively, are obtained. a reacts with HgCl₂ to (me₃Si)₂P? P(Sime₃)₂. (me₃Si)₃P can be cleaved with ClP(C₆H₅)₂ and ClPme₂ yielding (me₃Si)₂P? P(C₆H₅)₂ and (me₃Si)₂P? Pme₂, respectively. The ¹H- and ³¹P-n.m.r. and mass spectroscopic data are reported.     

Metallation studies of organofunctional trisiloxanes

Summary The organofunctional trisiloxanes Me₃SiOSiMe(R)OSiMe₃ [R=(CH₂)₂PPh₂, (CH₂)₃C₅H₄N, (CH₂)₃CN, (CH₂)₂Ph, (CH₂)₂SPh, CH=CH₂ and CH₂CH=CH₂] have been reacted with metal halide and-carbonyl moieties in order to determine the coordination preferences of materials being used as models for metallated longchain linear functionalised polysiloxanes. The products [Me₃SiOSiMe(R)OSiMe₃]₃ML_n [R=(CH₂)₂PPh₂, ML_n=RhCl],cis-[Me₃SiOSiMe(R)OSiMe₃]₂ML_n [R=(CH₂)₂PPh₂ or (CH₂)₃C₅H₄N, ML_n=Mo(CO)₄],trans-[Me₃SiOSiMe(R)OSiMe₃]₂ML_n[R=(CH₂)₂PPh₂, ML_n=NiCl₂, PdCl₂, PtCl₂ and [Rh(CO)Cl] and [Me₃SiOSiMe(R)OSiMe₃]ML_n [R=(CH₂)₂PPh₂, ML_n=Mo(CO)₃(2,2-bipyridine); R=(CH₂)₂Ph, ML_n=Mo(CO)₃; R=(CH₂)₃C₅H₄N, (CH₂)₃CN, or (CH₂)₂SPh, ML_n=Rh(CO)₂Cl; R=CH=CH₂ or CH₂CH=CH₂, ML_n=Fe(CO)₄] have been isolated and characterised spectroscopically in the course of these studies.     

Phase ratios in the K2O-V2O4-SO3 system at high sulfur trioxide concentrations

Phase ratios in the three-component oxide system K₂O-V₂O₄-SO₃ in the region of the sulfur trioxide concentrations corresponding to its concentrations in the active component of vanadium catalysts for SO₂ to SO₃ conversion have been studied using powder X-ray diffraction, IR spectroscopy, microscopy, and chemical analysis. Four individual compounds (K₂VO(SO₄)₂, K₂(VO)₂(SO₄)₃, K₂VO(SO₄)₂S₂O₇, and K₂(VO)₂(SO₄)₂S₂O₇) and K₂(VO)₂(SO₄)₂S₂O₇ and VOSO₄-base solid solutions of composition K₂(VO)_2+x (SO₄)_2+x S₂O₇ (0 ≤ x ≤ 1.5) were found in the system. K₂VO(SO₄)S₂O₇ and K₂(VO)₂(SO₄)₂S₂O₇ lose their sulfur trioxide when heated above 350°C under an inert atmosphere, and convert to K₂VO(SO₄)₂ and K₂(VO)₂(SO₄)₃, respectively. This implies that K₂VO(SO₄)₂S₂O₇ and K₂(VO)₂(SO₄)₂S₂O₇, as well as K₂(VO)_2+x (SO₄)_2+x S₂O₇ solid solution, cannot exist in the active component of real industrial catalysts.     

Synthesen und Kristallstrukturen neuer heterobimetallischer Tantal‐Münzmetall‐Chalkogenido‐Cluster

Syntheses and Crystal Structures of Novel Heterobimetallic Tantalum Coin Metal Chalcogenido Clusters In the presence of phosphine the thiotantalats (Et₄N)₄[Ta₆S₁₇] · 3MeCN reacts with copper to give a number of new heterobimetallic tantalum copper chalcogenide clusters. These clusters show metal chalcogenide units some of which here already known from the chemistry of vanadium and niobium. New Ta—M‐chalcogenide clusters could also be synthesised by reaction of TaCl₅ and silylated chalcogen reagents with copper or silver salts in presence of phosphine. Such examples are: [Ta₂Cu₂S₄Cl₂(PMe₃)₆] · DMF ( 1 ), (Et₄N)[Ta₃Cu₅S₈Cl₅(PMe₃)₆] · 2MeCN ( 2 ), (Et₄N)[Ta₉Cu₁₀S₂₄Cl₈(PMe₃)₁₄] · 2MeCN ( 3 ), [Ta₄Cu₁₂Cl₈S₁₂(PMe₃)₁₂] ( 4 ), (Et₄N)[Ta₂Cu₆S₆Cl₅(PPh₃)₆] · 5MeCN ( 5 ), (Et₄N)[Ta₂Cu₆S₆Cl₅(PPh₂Me)₆] · 2MeCN ( 6 ), (Et₄N)[Ta₂Cu₆S₆Cl₅(P^tBu₂Cl)₆] · MeCN ( 7 ) [Ta₂Cu₂S₄Br₄(PPh₃)₂(MeCN)₂] · MeCN ( 8 ), [Cu(PMe₃)₄]₂[Ta₂Cu₆S₆(SCN)₆(PMe₃)₆] · 4MeCN ( 9 ), [TaCu₅S₄Cl₂(dppm)₄] · DMF ( 10 ), [Ta₂Cu₂Se₄(SCN)₂(PMe₃)₆] ( 11 ), [Cu(PMe₃)₄]₂[Ta₂Cu₆Se₆(SCN)₆(PMe₃)₆] · 4MeCN ( 12 ), [TaCu₄Se₄(PⁿPr₃)₆][TaCl₆] ( 13 ), [Ta₂Ag₂Se₄Cl₂(PMe₃)₆] · MeCN ( 14 ), _∞[TaAg₃Se₄(PMe₃)₃] ( 15 ). The structures of these compounds were obtained by X‐ray single crystal structure analysis.     

Synthesis of Inorganic Structural Isomers By Diffusion‐Constrained Self‐Assembly of Designed Precursors: A Novel Type of Isomerism

The structure of precursors is used to control the formation of six possible structural isomers that contain four structural units of PbSe and four structural units of NbSe₂: [(PbSe)_1.14]₄[NbSe₂]₄, [(PbSe)_1.14]₃[NbSe₂]₃[(PbSe)_1.14]₁[NbSe₂]₁, [(PbSe)_1.14]₃[NbSe₂]₂[(PbSe)_1.14]₁[NbSe₂]₂, [(PbSe)_1.14]₂[NbSe₂]₃[(PbSe)_1.14]₂[NbSe₂]₁, [(PbSe)_1.14]₂[NbSe₂]₂[(PbSe)_1.14]₁[NbSe₂]₁[(PbSe)_1.14]₁[NbSe₂]₁, [(PbSe)_1.14]₂[NbSe₂]₁[(PbSe)_1.14]₁[NbSe₂]₂[(PbSe)_1.14]₁[NbSe₂]₁. The electrical properties of these compounds vary with the nanoarchitecture. For each pair of constituents, over 20 000 new compounds, each with a specific nanoarchitecture, are possible with the number of structural units equal to 10 or less. This provides opportunities to systematically correlate structure with properties and hence optimize performance.     

Acetylenic derivatives of metal carbonyls of the triad Fe,Ru, Os—XI Mass spectra of some binuclear complexes

The mass spectra of the following acetylenic derivatives of iron, ruthenium and osmium carbonyls are reported: the iron compounds Fe₂(CO)₆[C₂(C₆H₅)s₂]₂, Fe₂(CO)₆[C₂(CH₃)₂]₂ and Fe₂(CO)₆[C₂(C₂H₅)₂]₂, the ruthenium compounds Ru₂(CO)₆[C₂(C₆H₅)₂]₂, and Ru₂(CO)₆[C₂(CH₃)₂]₂ and the osmium compounds Os₂(CO)₆[C₂(C₆H₅)₂]₂, Os₂(CO)₆[C₂HC₆H₅]₂ and Os₂(CO)₆[C₂(CH₃)₂]₂. Iron compounds exhibit breakdown schemes where binuclear, mononuclear and hydrocarbon ions are present. On the other hand, ruthenium and osmium compounds fragment in a similar way and give rise to singly and doubly charged binuclear ions. Phenylic derivatives of ruthenium and osmium also give weak triply charged ions. The results are discussed in terms of relative strengths of the metal-metal and metal-carbon bonds.     

Darstellung von polyfluororganotrichlorsilanen

The following substances could be prepared by Grignard reactions or by conversions with trichlorosilane: C₆F₅CH₂CHCH₂, C₆F₅(CH₂)₃SiCl₃, CF₃(CF₂)₉CH₂CHCH₂, CF₃(CF₂)₇(CH₂)₂SiCl₃, CF₃(CF₂)₁₁(CH₂)₃CHCH₂ und CF₃(CF₂)₁₁(CH₂)₅SiCl₃.They were characterized by spectroscopical and microanalytical methods.     

Mass spectra of organometallic compounds—VII; Organonitrogen derivatives of metal carbonyls

The positive-ion mass spectra of the following organonitrogen derivatives of metal carbonyls are discussed: (i) The compounds NC₅H₄CH₂Fe(CO)₂C₅H₅, NC₅H₄CH₂COMo(CO)₂C₅H₅, NC₅H₄CH₂W(CO)₃C₅H₅, NC₅H₄CH₂COMn(CO)₄, C₅H₁₀NCH₂CH₂Fe(CO)₂C₅H₅, (CH₃)₂NCH₂CH₂COFeCOC₅H₅ and (CH₃)₂NCH₂CH₂COMn(CO)₄ obtained from metal carbonyl anions and haloalkylamines, (ii) The isocyanate derivative C₅H₅Mo(CO)₃CH₂NCO; (iii) The arylazomolybdenum derivatives RN₂Mo(CO)₂C₅H₅ (R ? phenyl, p-tolyl, or p-anisyl); (iv) The compound (C₆H₅N)₂COFe₂(CO)₆ obtained from Fe₃(CO)₁₂ and phenyl isocyanate; (v) The N,N,N′,N′-tetramethylethylenediamine complex (CH₃)₂NCH₂CH₂N(CH₃)₂W(CO)₄. Further examples of eliminations of hydrogen, CO, and C₂H₂ fragments were noted. In addition evidence for the following more unusual processes was obtained: (i) Elimination of HCN fragments from the ions [NC₅H₄CH₂MC₅H₅]⁺ to give the ions [(C₅H₅)₂M]⁺ (M ? Fe, Mo and W); (ii) Conversion of C₅H₅Mo(CO)₃CH₂NCO to C₅H₅Mo(CO)₂CH₂NCO within the mass spectrometer; (iii) Elimination of N₂ from [RN₂MoC₅H₅]⁺ to give [RMoC₅H₅]⁺; (iv) Novel eliminations of HNCO, FeNCO, and C₆H₅NC fragments in the mass spectrum of (C₆H₅N)₂COFe₂(CO)₆; (v) Facile dehydrogenation of the N,N,N′,-N′-tetramethylethylenediamine ligand in the complex (CH₃)₂NCH₂CH₂N(CH₃)₂W(CO)₄.     

Beiträge zur Untersuchung anorganischer nichtstöchiometrischer Verbindungen. XXXIII. Darstellung und elektronenmikroskopische Untersuchung von Hf2Nb20O54, M3Nb44O116 und MNb24O62 (M = Zr,Hf)

Contributions to the Investigation of Inorganic Non-stoichiometric Compounds. XXXIII. Preparation and Electron Microscopical Investigation of Hf₂Nb₂₀O₅₄, M₃Nb₄₄O₁₁₆, and MNb₂₄O₆₂ (M = Zr, Hf) The phases Hf₂Nb₂₀O₅₄, Zr₃Nb₄₄O₁₁₆, Hf₃Nb₄₄O₁₁₆, and β-HfNb₂₄O₆₂ have been prepared for the first time. The oxides MO₂ (M = Zr, Hf) and Nb₂O₅ were fused with (NH₄)₂SO₄ and their mixed precipitations were heated at 1350°C. In the same way we also obtained pure β-ZrNb₂₄O₆₂. The new compounds have block structures, as the structure investigation with HRTEM shows. Hf₂Nb₂₀O₅₄ is isostructural with Nb₂₂O₅₄, the same is valid for Zr₃Nb₄₄O₁₁₆ and Hf₃Nb₄₄O₁₁₆ with respect to Nb₄₇O₁₁₆. β-HfNb₂₄O₆₂ has the same structure as β-ZrNb₂₄O₆₂ and β-Nb₂₅O₆₂.     

Dimethylphosphinato and dimethylarsinato complexes of Sb(III) and Bi(III) and their chemistry

Abstract  

The reaction of Me₂PO₂H and Me₂AsO₂H with SbCl₃, BiCl₃, and Bi(NO₃)₃·5H₂O gave the complexes Sb(Me₂PO₂)₃, Sb(Me₂AsO₂)₃, (Me₂PO₂)₂Bi-Cl, Bi(Me₂AsO₂)₃, (Me₂PO₂)₂Bi(NO₃), and (Me₂AsO₂)₂Bi(NO₃)·H₂O, respectively. The arsinato complexes did not react with the Lewis bases pyridine, Ph₃P, and Ph₃As in acetone. The compounds Sb(Me₂AsO₂)₃ and (Me₂AsO₂)₂Bi(NO₃)·H₂O reacted to a small extent with nicotinic acid in methanol but Bi(Me₂AsO₂)₃ gave (Me₂AsO₂-BiO) _x in good yields. (Me₂AsO₂)₂Bi(NO₃)·H₂O in methanol quantitatively rearranged to new complexes with the same composition, [(Me₂AsO₂)₂Bi(NO₃)·H₂O]′ and [(Me₂AsO₂)₂Bi(NO₃)·H₂O]″ in the presence of pyridine. With thiophenol in air, Sb(Me₂AsO₂)₃ gave PhSSPh and Me₂As-SPh (1:1 mol ratio), (Me₂AsO₂-SbO) _x and some Sb(Me₂AsO₂)₃ was reformed, Bi(Me₂AsO₂)₃ gave (Me₂AsO₂-BiO) _x , PhSSPh, and Me₂As-SPh (1:0.6 mol ratio), whereas (Me₂AsO₂)₂Bi(NO₃)·H₂O quantitatively gave PhSSPh, thus acting as a catalyst for the air oxidation of thiophenol.     

Reaktionen von R4Sb2 (R = Me,Et) mit (Me3SiCH2)3M (M = Ga,In) und Kristallstrukturen von [(Me3SiCH2)2InSbMe2]3 und [(Me3SiCH2)2GaOSbEt2]2

Reactions of R₄Sb₂ (R = Me, Et) with (Me₃SiCH₂)₃M (M = Ga, In) and Crystal Structures of [(Me₃SiCH₂)₂InSbMe₂]₃ and [(Me₃SiCH₂)₂GaOSbEt₂]₂ The reaction of (Me₃SiCH₂)₃In with Me₂SbSbMe₂ gives [(Me₃SiCH₂)₂InSbMe₂]₃ ( 1 ) and Me₃SiCH₂SbMe₂. [(Me₃SiCH₂)₂GaOSbEt₂]₂ ( 2 ) is formed by the reaction of (Me₃SiCH₂)₃Ga with Et₂SbSbEt₂ and oxygen. The syntheses and the crystal structures of 1 and 2 are reported.