- NMR study of the interaction of tin(II) and antimony(III) fluorides with phosphorus chlorides
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Reactions of SnF2 and SbF3 with POCl3 and PCl5 in acetonitrile were studied by 19F, 31P, and 119Sn NMR. Tetrahedral compounds POF2Cl and POF 3 form in the r
- Kokunov,Ershova,Razgonyaeva
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- Chloro(trifluorophosphane)gold(I): [Au(PF3)Cl]
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X-ray quality crystals of [Au(PF3)Cl] (orthorhombic, Pnma) are obtained from a toluene / pentane solution at 6 °C. According to the result of the X-ray structural analysis, [Au(PF3)Cl] contains an almost linear F3P-Au-Cl u
- Schoedel, Frauke,Bolte, Michael,Wagner, Matthias,Lerner, Hans-Wolfram
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- Thermal behavior of ferrous diffuorodioxophosphates
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Difluorodioxophosphates may be used as ceramic phosphate precursor, and their thermal behaviours are very important. In this paper we study by TG and DTA the thermal stability for iron(II) salt. In argon atmosphere, we obtain in a first time the melting of salt at 240°C then the classical breaking up into solid orthophosphate and POF3 exhaust. If the sample of iron(II) difluorodioxophosphate is heating in air, we do not obtain the melting phenomena, but at the same temperature an exothermic phenomenon that conducts to the formation of iron(III). We observe a mass increase. By IR analysis, we can show that this oxidation is obtained without change of difluorodioxophosphate structure.
- Vast,Semmoud
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- Crystal structure and spectroscopic investigations of POF3
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Phosphoryl fluoride was characterized by Raman spectroscopy and X-ray diffraction analysis. The X-ray structure was obtained by in-situ crystallization. Phosphoryl fluoride crystallizes in the trigonal space group Pβar{3}μ1 with two formula units in the unit cell. In the crystal structure zigzag chains are observed which are formed by intermolecular P-O contacts. The Raman spectra of neat and matrix isolated POF3 display an extra line, which indicates intermolecular interaction in the solid state. Therefore quantum chemically calculation of a POF3 oligomer was performed. The theoretical calculation indicates that the extra Raman line is caused by side splitting of the P-O valence vibration.
- Feller, Michael,Lux, Karin,Kornath, Andreas
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- In pursuit of the PO2+ cation. The reaction of KPO2F2 and SbF5 leads to an eight-membered antimony-oxygen-phosphorus-bridged ring
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The reaction of KPO2F2 with the strong Lewis acid SbF5 was studied as a potential pathway to the unknown PO2+ cation. The resulting product has the desired PO2SbF6 composition but consists of an eight-membered, antimony-oxygen-phosphorus-bridged ring that was characterized by vibrational and NMR spectroscopy, ab initio methods, and a single crystal x-ray diffraction study. The preferred formation of the ring and its mechanism are discussed. Wiley-VCH Verlag GmbH, 2001.
- Schneider, Stefan,Vij, Ashwani,Sheehy, Jeffrey A.,Tham, Fook S.,Schroer, Thorsten,Christe, Karl O.
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- The gas-phase on-line production of phosphoryl halides, POX3 and their identification by infrared spectroscopy
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A new route has been devised, leading to the production of POX3 molecules where X = F, Br and I by an on-line process using phosphoryl chloride, POCl3 as a starting material passed over heated sodium fluoride, NaF, potassium bromide, KBr and potassium iodide, KI at 535, 690 and 480°C, respectively. The products have been characterised by the infrared (IR) spectra of their vapours. The low resolution gas-phase Fourier transform infrared spectra reported for the first time show strong bands centered at 1416.6, 1312.9, 1297.9 and 1285 cm-1, assigned to ν1(a1), the O=P stretching fundamental of POF3, POCl3, POBr3 and POI3, respectively.
- Allaf, Abdul W.
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- Initial stages of thermal decomposition of LiPF6-based lithium ion battery electrolytes by detailed Raman and NMR spectroscopy
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Independent of the specific electrode chemistry, the state-of-the-art lithium ion battery electrolytes based on LiPF6 in organic solvents have a low thermal abuse tolerance and poor cycle life at elevated temperatures. We present here a detailed investigation of the initial stages of the thermal decomposition of LiPF6 in EC/DMC stored at 85 °C using Raman and NMR spectroscopy. During storage (up to 160 h), significant amounts of CO 2 are evolved, as detected in the Raman spectra. Time-resolved 1H, 31P, and 19F NMR spectra show the evolution of POF3, POF(OH)2, POF2(OCH2CH 2)nF, and POF2OMe as reactive decomposition products. Our unique 19F NMR approach, measuring while heating with both high energy and time resolution, allows for a first quantitative analysis of the evolved species and reveals several decomposition reactions during the first 30 min up to 72 h, where the rates of HF and POF2OMe formation are surprisingly linear. EC is found to be much less reactive compared to DMC. All information is used in the formulation of an updated decomposition pathway chart for LiPF6 based electrolytes. The Royal Society of Chemistry 2013.
- Wilken, Susanne,Treskow, Marcel,Scheers, Johan,Johansson, Patrik,Jacobsson, Per
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- Decomposition of fluorophosphoryl diazide: A joint experimental and theoretical study
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The photolytic and thermal decomposition of fluorophosphoryl diazide, FP(O)(N3)2, was studied using matrix isolation spectroscopy. Upon ArF laser photolysis (λ = 193 nm), FPO and a new geminal azido nitrene FP(O)(N3)N were identified using matrix IR spectroscopy. The nitrene shows a triplet ground state with the zero-field parameters D/hc = 1.566 cm-1 and E/hc = 0.005 cm-1. Further decomposition of the nitrene into FPO was observed under an irradiation of λ > 335 nm. In contrast, no nitrene but only FPO was identified after flash vacuum pyrolysis of the diazide. To reveal the decomposition mechanism, quantum chemical calculations on the potential energy surface (PES) of the diazide using DFT methods were performed. On the singlet PES four conformers of the nitrene were predicted. The two conformers (syn and anti) showing intramolecular Nnitrene...Nα,azide interactions are much lower in energy (ca. 40 kJ mol-1, B3LYP/6-311+G(3df)) than the other two exhibiting Nnitrene...O interactions. syn/anti refers to the relative orientation of the PO bond and the N3 group. The interconversion of these species and the decomposition into FPO via a novel three-membered ring diazo intermediate cyclo-FP(O)N2 were computationally explored. The calculated low dissociation barrier of 45 kJ mol-1 (B3LYP/6-311+G(3df)) of this cyclic intermediate rationalizes why it could not be detected in our experiments. This journal is
- Li, Dingqing,Li, Hongmin,Zhu, Bifeng,Zeng, Xiaoqing,Willner, Helge,Beckers, Helmut,Neuhaus, Patrik,Grote, Dirk,Sander, Wolfram
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p. 6433 - 6439
(2015/04/21)
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- Ligand-interchange reactions between M(iv) (M = Ti, V) oxide bis-acetylacetonates and halides of high-valent group 4 and 5 metals. A synthetic and electrochemical study
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The reactions of M′O(acac)2 [M′ = Ti, V; acac = acetylacetonato anion] with equimolar amounts of MF5 (M = Nb, Ta) in CH2Cl2 afforded Ti(acac)2F2, 1a, and [V(acac)3][MF6] (M = Nb, 4a; M = Ta, 4b), respectively. MOF3 (M = Nb, 2a; M = Ta, 2b) were co-produced from MF 5/TiO(acac)2. The intermediate species [TaF 4{OTi(acac)2}2][TaF6], 3, was intercepted in the course of the formation of 1a from TiO(acac) 2/TaF5. NbCl5 reacted with TiO(acac) 2 yielding selectively the previously reported [NbO(acac)Cl 2]x, 5, and Ti2(acac)2(μ-Cl) 2Cl4, 6. Complex 6 was alternatively obtained from the addition of a two-fold excess of TiCl4 to VO(acac)2. The 1 : 1 reactions of TiX4 (X = F, Cl) with TiO(acac)2 in dichloromethane gave Ti(acac)2X2 (X = F, 1a; X = Cl, 1b) and TiOX2 (X = F, 7a; X = Cl, 7b). The 1 : 1 combination of TiX 4 (X = F, Cl) with VO(acac)2 led to 1a,b and VOX 2 (X = F, 8a; X = Cl, 8b). The μ-oxido compounds (C 6F5)3B-O-M′(acac)2 (M′ = Ti, V) underwent fragmentation by [PF6]- in chlorinated solvent, yielding POF3, 9, and [B(C6F5) 3F]-, 10, according to NMR studies; 1a and V(acac) 3+, respectively, were detected as the metal-containing species. Electrochemical studies were carried out aiming at the full characterization of the products and the observation of possible degradation pathways.
- Funaioli, Tiziana,Marchetti, Fabio,Pampaloni, Guido,Zacchini, Stefano
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p. 14168 - 14177
(2013/10/01)
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- Matrix isolation and theoretical study of the reaction of substituted phosphines with CrCl2O2
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The reactions between CrO2Cl2 and a series of substituted phosphines have been investigated using matrix isolation infrared spectroscopy. For all of the phosphines except PF3, twin jet co-deposition of the two reagents into argon matrices at 14 K initially led to the formation of weak bands due to the corresponding phosphine oxide. For all of the phosphines, subsequent irradiation with light of λ > 300 nm led to the growth of a number of intense new bands that have been assigned to the phosphine oxide complexed to CrCl2O, following an oxygen atom transfer reaction. Gas-phase, merged jet reactions prior to matrix deposition led to a significant yield of the uncomplexed phosphine oxide. Theoretical calculations at the B3LYP/6-311++g(d,2p) level were carried out in support of the experimental work, to support product band assignments and clarify the nature of the molecular complexes.
- Delson, Adam J.,Ault, Bruce S.
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p. 13786 - 13791
(2008/10/09)
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- Thermal decomposition of LiPF6-based electrolytes for lithium-ion batteries
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The thermal decomposition of lithium-ion battery electrolytes 1.0 M LiPF6 in one or more carbonate solvents has been investigated. Electrolytes containing diethyl carbonate (DEC), ethylene carbonate (EC), a 1:1 mixture of EC/dimethyl carbonate (DMC), and a 1:1:1 mixture EC/DMC/DEC have been investigated by multinuclear nuclear magnetic spectroscopy, gas chromatography with mass selective detection, and size exclusion chromatography. Thermal decomposition affords products including: carbon dioxide (CO 2), ethylene (CH2CH2), dialkylethers (R 2O), alkyl fluorides (RF), phosphorus oxyfiuoride (OPF3), fluorophosphates [OPF2OR, OPF(OR)2], fluorophosporic acids [OPF2OH, OPF(OH)2], and oligoethylene oxides. The mechanism of decomposition is similar in all LiPF6/carbonate electrolytes. Trace protic impurities lead to generation of OPF2OR, which autocatalytically decomposes LiPF6 and carbonates. The presence of DEC leads to the generation of ethylene, while the presnce of EC leads to the generation of capped oligothylene oxides [OPF2(OCH 2CH2)nF].
- Campion, Christopher L.,Li, Wentao,Lucht, Brett L.
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p. A2327-A2334
(2008/10/09)
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- Synthesis of phosphoryl fluoride
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Gas-phase hydrolysis of phosphorus pentafluoride constitutes the basis for phosphoryl fluoride synthesis. We propose a procedure for phosphorus pentafluoride hydrolysis in a flow system, followed by adsorption of hydrogen fluoride in a column packed with granulated sodium fluoride. We show that POF3 can be freed from HF to a level of lower than 0.1 vol %. A flow setup is designed to produce up to 40 g of phosphoryl fluoride per hour. It is established that the occurrence of side reactions (accompanying the major reaction PF5 + H2O → POF3 + HF) is responsible for the decreased yield. Copyright
- Artyukhov,Kravets,Udalova
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p. 157 - 160
(2008/10/08)
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- Synthesis of Yb3+-activated Strontium Fluorapatite
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Sr5(PO4)3F:Yb3+, a candidate material for gain media, was synthesized by solid-state reaction. Results of chemical analysis, x-ray diffraction, and IR absorption spectroscopy confirm the formation of strontium fluorapatite. Substitution of F- for OH- via fluorination of Sr5(PO4)3OH in hydrofluoric acid or hydrogen fluoride gas leads to the formation of strontium fluoride and phosphorus pentafluoride or oxyfluoride.
- Orlovskii,Zhigarnovskii,Rodicheva,Popov,Romanova,Kharsika
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p. 391 - 394
(2008/10/08)
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- The [PO2F2?2AsF5]- anion, an example of a stable, oxygen-bridged, 1:2 donor-acceptor polynuclear anion
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KPO2F2 reacts at room temperature with excess AsF5 in a 1:2 mol ratio. The resulting stable white product was characterized by vibrational and multinuclear NMR spectroscopy in the solid state and SO2 solution, respectively. It is shown that AsF5 neither displaces PO2F from KPO2F2, nor generates PO2+AsF6-, but forms a stable, oxygen-bridged polynuclear [PO2F2?2AsF5]- anion. When pyrolyzed, this anion undergoes a stepwise decomposition to KAsF6, POF3 and AsOF3, followed by the decomposition of KAsF6 to KF and AsF5. While [PO2F2?2AsF5]- is stable in SO2 solution, it decomposes in CD3CN solution to the known CD3CN?AsF5 adduct and [PO2F2?AsF5]- anion. The inability of AsF5 to displace PO2F from its salts confirms that the latter is a very strong Lewis acid which is comparable in strength to AsF5. With PF5 the KPO2F2 salt forms at -78°C the 1:2 adduct K[PO2F2?2PF5], which on warm-up to room temperature loses 1 mol of PF5 to give the 1:1 adduct, K[PO2F2?PF5]. The 1:1 adduct is marginally stable at room temperature and undergoes slow POF3 evolution. An improved synthesis of POF3 from PF5 and P4O10 is reported. Gauthier-Villars.
- Christe,Gnann,Wagner,Wilson
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p. 865 - 877
(2008/10/08)
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- Low temperature fluorination of some non-metals and non-metal compounds with fluorine
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Low temperature fluorination with elemental fluorine of elemental phosphorus, sulphur, silicon, amorphous carbon and phosphorus trichloride, phosphorus pentoxide, triphenylphosphine, hexafluorodisilane, hexachlorodisilane, hexabromodisilane, tetrasulphur tetranitride, sulphur dioxide, thionyl chloride and sulphuryl chloride has been carried out in freon-11 medium.The corresponding fluoro compounds have been isolated in near quanititative yields, purified by low temperature fractional condensation and characterised by IR spectroscopy and elemental analysis.
- Padma, D K,Kalbandkeri, R G,Suresh, B S,Bhat, V Subrahmanya
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p. 172 - 176
(2007/10/02)
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- Thermodynamic properties of uranyl fluorophosphates
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The decomposition of uranyl di- and monofluorophosphates has been studied tensimetrically.The formation of a compound, (UO2(PO2F2)F, has been detected in the UO2F2-UO2(PO2F2)2 system.The thermodynamic characteristics of the decomposition of the uranyl di- and monofluorophosphates have been determined according to the second and third law of thermodynamics.The results have been used to calculate the enthalpies of formation ΔfH(298 K) of the compounds UO2(PO2F2)2, UO2(PO2F2)F, and UO2PO3F.
- Petrov, V. G.,Seleznev, V. P.,Gubchkin, B. A.
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p. 1066 - 1068
(2007/10/02)
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- OXIDATION OF PHOSPHORUS(III) HALIDES BY RED PHOTOLYSIS OF OZONE COMPLEXES IN SOLID ARGON
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PCl3-O3 and PBr3-O3 complexes in solid argon photolyze to give phosphoryl halides with red visible radiation that has no effect on isolated ozone.These observations and similar results for PH3-O3 and P4-O3 complexes show that the complex markedly increases the cross section for red photodissociation of ozone and suggest that this increase is due to the complex effectively lowering the barrier to dissociation by providing a strongly exothermic dissociation-recombination process.
- Moores, Brian W.,Andrews, Lester
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p. 1902 - 1907
(2007/10/02)
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- Investigations of Solid State Reactions of Binary Polyphosphate-Fluoride Systems by Means of Thermal Analysis, X-Ray Diffraction and NMR Spectroscopy. - IV. Systems M(PO3)3 + MF3 (M = Al, La)
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The reactions of Al(PO3)3 with AlF3 and of La(PO3)3 with LaF3 can mainly be described by the formula: .As function of the temperature the tridymite-like modification of AlPO4 (? = 30.7 ppm), the cristobalite-like form (? = 27.8 ppm) and berlinite (? = 25.4 ppm) are found both by NMR and X-ray investigations.The 31P chemical shift parameters of LaPO4 are: ? = (5.7 +/- 0.5)ppm, Δ? = (15 +/- 5) ppm and η ca. 1. - Keywords: NMR (MAS) in solids / Solid state reactions / Phosphate-fluoride systems
- Ehrt, D.,Jaeger, C.
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- Matrix Photochemistry of Hypofluorous Acid HOF: Oxygen Atom Transfer and Other Reactiuons
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The infrared spectrum of the hypofluorous acid molecule, HOF, trapped in different solid matrices at low temperatures shows that the vibrational fundamentals ν1 and ν2 are perturbed to extents that vary with the basicity of the adjac
- Appelman, Evan H.,Downs, Anthony J.,Gardner, Christopher J.
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p. 598 - 608
(2007/10/02)
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- Investigations of Solid State Reactions of Binary Polyphosphate-Fluoride Systems by Means of Thermal Analysis, X-Ray Diffraction and NMR Spectroscopy. V. Reactions of Sr(PO3)2 with AlF3, CaF2 and MgF2
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In the system Sr(PO3)2 + 4 AlF3 the polyphosphate is decomposed to Sr2P2O7, AlPO4 and SrAlF5 at 600 degC.The final products are mainly AlPO4 and SrAlF5, few apatite Sr5F(PO4)3 is formed.In the system Sr(PO3)2 + 5 CaF2 the reaction rate is distinctly slower.Sr2P2O7, Ca2P2O7 and Ca5F(PO4)3 are formed as solid phases.Even after 24 h at 600 degC Sr(PO3)2 is still found in the system Sr(PO3)2+ MgF2. β-Mg2P2O7 and α-Sr2P2O7 are formed.The reaction rate is very slow. - Keywords: NMR (MAS) in solids / Solid state reactions / Phosphate-Fluoride systems
- Jaeger, C.,Ehrt, D.
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p. 109 - 118
(2007/10/02)
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- Gas-Phase Lewis Acid-Base Interactions. An Experimental Determination of Cyanide Binding Energies from Ion Cyclotron Resonance and High-Pressure Mass Spectrometric Equilibrium Measurements
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Both ion cyclotron resonance and high-pressure mass spectrometric equilibrium techniques have been used to investigate the binding energies of anions to a variety of Lewis acids.From an analysis of the enthalpy changes associated with CN- binding it is evident that in cases of relatively weak binding considerable freedom of rotational motion of CN- in the complex may be retained.Ab initio calculations and experiment suggest that binding through both the N and C sites of CN- is nearly equally favorable in some cases.In contrast to results previously obtained for Bronsted acids which showed that CN- and Cl- bind nearly identically, the present data for Lewis acids show many cases where cyanide is much more favorably bound than chloride, a consequence of enhanced covalent binding of the CN- complexes.New Kroeger Drago parameters derived for CN- support the importance of covalent binding in cyanide adducts.Correlations of binding energy of anions to Lewis acids with the anion proton affinity show excellent linear relationships which may be used to predict binding energetics for new anions.
- Larson, J. W.,Szulejko, J. E.,McMahon, T. B.
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p. 7604 - 7609
(2007/10/02)
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- Investigations of Solid State Reactions of Binary Polyphosphate - Fluoride Systems by Means of Thermal Analysis, X-Ray Diffraction and NMR Spectroscopy. III. System Mg(PO3)2 + MgF2
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The solid state reactions of the system Mg(PO3)2 + MgF2 can be described by the global scheme: .Contrary to the system M(PO3)2 + MF2 (M: Ba, Sr, Ca) a monophosphate, Mg3(PO4)2, and a special apatite, Mg2FPO4, are formed. - Keywords: NMR (MAS) in solids / Solid state reactions / Phosphate-fluoride systems
- Jaeger, C.,Ehrt, D.
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p. 103 - 112
(2007/10/02)
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- Investigations of Solid State Reactions of Binary Polyphosphate - Fluoride Systems by Means of Thermal Analysis, X-Ray Diffraction and NMR Spectroscopy. II. Systems Sr(PO3)2 + SrF2 and Ca(PO3)2 + CaF2
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The high temperature solid state reactions of the mixtures M(PO3)2 + MF2 (M=Sr,Ca) have been studied.The reactions can be described as follows: .The expected intermediate product MPO3F is not observed.The reasons are discussed. - Keywords: NMR (MAS) in solids / Solid state reactions / Phosphate-fluoride systems
- Ehrt, D.,Jaeger, C.
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- Investigations of Solid State Reactions of Binary Polyphosphate - Fluoride Systems by Means of Thermal Analysis, X-Ray Diffraction and NMR Spectroscopy. I. System Ba(PO3)2 + BaF2
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The high temperature reactions of the mixture Ba(PO3)2 + BaF2 have been studied.In the temperature range 600...700 deg C the reaction can be described by: Ba(PO3)2 + BaF2 -> 2 BaPO3F.Besides this the fluorophosphate is further decomposed in the temperature range 900...1400 deg C: 5 BaPO3F -> 2 Ba2P2O7 + BaF2 + POF3 . - Keywords: NMR (MAS) in solids / Solid state reactions / Phosphate-fluoride systems
- Jaeger, C.,Ehrt, D.,Haubenreisser, U.
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- Photochemistry of Low-Temperature Matrices Containing Carbonyl Sulfide: Reactions of Sulfur Atoms with the Phosphorus Trihalides PF3 and PCl3 and the Hydrocarbons CH4, C2H4, and C2H2
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Exposure of a solid argon matrix containing the molecules OCS and PX3 (X = F or Cl) at ca. 20 K to broad-band ultraviolet radiation leads to the formation of CO and the corresponding thiophosphorus(V) halides SPX3, as witnessed by the infrared spectrum of the matrix.Photolysis of a solid methane matrix containing OCS at 13-20 K on exposure to radiation with wavelengths near 230 nm gives rise to CO, methanethiol, CH3SH, thioformaldehyde, H2C=S, and carbon disulfide, CS2, as the only products to be detected by their infrared spectra.Yet there is no sign of either CH3SH or H2C=S on photolysis of OCS in a CH4-doped argon matrix with the composition Ar:CH4:OCS = 100:20:1.Evidently the photolysis of OCS generates 1D sulfur atoms which add to an adjacent CH4 molecule with the formation of a vibrationally activated intermediate *; this relaxes to give CH3SH or decomposes to give H2C=S.Similar experiments have been carried out with solid argon matrices including OCS and either C2H4 or C2H2.In the presence of C2H4 there is no hint of C-H insertion; instead the C2H4 undergoes sulfur atom addition at the double bond to give thiirane, , as the sole product to be identified by its infrared spectrum.By contrast, C2H2 yields thioketene, H2C=S, ethynethiol, HCCSH, and carbon disulfide, CS2, as the main products, as well as thiirane, , as a minor product.The response of the hydrocarbon molecules in argon matrices can be interpreted in terms of the diffusion and reaction of ground-state 3P sulfur atoms but not of 1D sulfur atoms which are too short-lived to undergo significant migration.It appears that 3P sulfur atoms react with both C2H4 and C2H2 to yield a triplet diradical: that derived from C2H4 favors cyclization, whereas that derived from C2H2 rearranges preferentially to H2C=C=S and this in turn enters into secondary reactions to give HCCSH and CS2.
- Hawkins, Michael,Almond, Matthew,Downs, Anthony J.
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p. 3326 - 3334
(2007/10/02)
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- SYNTHESIS OF METAL PHOSPHATES USING SiP2O7.
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A new, alternative route to the synthesis of metal phosphates by using silicon pyrophosphate as a reagent was studied. The reaction of silicon pyrophosphate with metal oxides yields a solid mixture of silica and metal phsophates; its reaction with metal flourides yields solid metal phosphates and gaseous mixtures of SiF//4 and POF//3.
- Bamberger,Begun,Heatherly
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p. c208-c209
(2008/10/08)
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- Oxygen atom transfer in low-temperature matrices. 1. Formation and characterization of matrix-isolated OMF3 (M = P, As)
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Ultraviolet photolysis of ozone isolated in a noble-gas matrix in the presence of the trifluoride MF3 (M = P, As) results in the formation of the corresponding trifluoride oxide, OMF3. The intensities and frequencies of the infrared absorptions due to the 16O- and 18O-substituted versions of the hitherto unknown molecule OAsF3 are consistent with the expected C3v symmetry. The vibrational spectra have been analyzed for information about the bonding in OAsF3, and an attempt has been made to estimate the bond angles on the basis of the intensities in infrared absorption of the bond-stretching fundamentals.
- Downs, Anthony J.,Gaskill, Geoffrey P.,Saville, Simon B.
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p. 3385 - 3393
(2008/10/08)
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- Oxidation of tris(trifluoromethyl)phosphine
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Oxygen reacts with tris(trifluoromethyl)phosphine by a chain reaction involving the trifluoromethyl radical and its autoxidation. With thermal quenching, tris(trifluoromethyl) phosphate and bis(trifluoromethyl)fluorophosphine oxide are formed. Under conditions of spontaneous ignition the latter compound delivers CF2, a powerful reducing agent.
- Mahler, Walter
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p. 352 - 354
(2007/10/05)
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