- Adduct compounds (MCl5)2(β-P4Ch 4) with M = Nb, Ta and Ch = S, Se
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Adduct compounds of the general composition (MCl5) 2(β-P4Ch4), M = Nb, Ta and Ch = S, Se, were obtained from solutions of M2Cl10 and P 4Ch3 in CS2 / n-hexan
- Hoppe, Diana,Pfitzner, Arno
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- The crystal and molecular structure of γ-P4S6
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The crystal and molecular structure of γ-P4S6 was determined from single-crystal X-ray diffraction. It crystallizes monoclinically in the space group P21/m (No. 11) with a = 6.627(3) A, b = 10.504(7) A, c = 6.878(3) A, β = 90.18(4)°, V = 478.8(4) A3, and Z = 2. The structure consists of cage-like P4S6 molecules with CS symmetry arranged with the topology of a cubic close packing. Copyright
- Roedl, Thomas,Pfitzner, Arno
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- Phosphorus chalcogen molecules as complex ligands - Reactions with NbCl5
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The reaction of P4E3 (E = S, Se) with NbCl5 yields [β-P4S4(NbCl5)2] and [P4Se3(NbCl5)]. [β-P4S4(NbCl5)2] crystallizes in the monoclinic space group P21/n with the lattice parameters a = 6.226(1), b = 12.971(2), c = 26.380(2) A, β = 93.7(1) (Z = 4). In this compound a sulfur atom is introduced into the basal P3-ring and the resulting β-P4S4 is central unit of the complex. [P4Se3(NbCl5)] crystallizes in the same space group type with the lattice parameters a = 11.939(1), b = 18.603(2), c = 12.763(4) A, β= 90.16(2)° (Z = 8). In both compounds the ligands are coordinated to basal phosphorus atoms.
- Nowottnick, Heike,Stumpf, Klaus,Blachnik, Roger,Reuter, Hans
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- Theoretical and spectroscopic investigation of coordination compounds from P4S3, copper(I) iodide and W(CO)5
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The formation of a new type of organometallic-inorganic hybrid coordination polymer from P4S3·W(CO)5 (1) and CuI has been studied. The structure of [P4S3·W(CO 5) (CuI) (3) has been verified by the combination of spectroscopic (IR, Ra-man, 31P MAS NMR) and X-ray diffraction methods. Theoretical studies of β-P4S3· P4S 3·W(CO)5 (1), 1D-(P4S3)(CuI) (2), and. 3D-(P4S3)(CuI)3 (4), which may be considered as poten-tial building blocks of 3, were carried out on the DFT level in the crystalline phase. The comparison of calculated and measured vibration modes of the P4S3 cage allows the unequivocal, assignment of the recorded. Raman shifts between 200 and 480 cm-1 and the determination of the degree of integration of P4S3 within the one-dimensional stacks of 2 or copper iodide networks of 3 and 4.
- Balazs, Gabor,Biegerl, Andreas,Groeger, Christian,Wachter, Joachim,Weihrich, Richard,Zabel, Manfred
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- Synthesis of cationic R2P5+ cages and subsequent chalcogenation reactions
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Cationic R2P5+ cage compounds (1 +) have been synthesized by the stoichiometric reaction of R 2PCl, GaCl3 and P4. The reaction conditions depend on the substituent R. Alkyl-substituted derivatives (1 a-1 d[GaCl 4]) are best synthesized under solvent-free conditions, whereas aryl-substituted derivatives (1 e-1 h[GaCl4]) are formed in C 6H5F. All compounds have been prepared on a multi-gram scale in good to excellent yields and have been fully characterized with an emphasis on 31P NMR spectroscopy in solution and single-crystal structure determination. Subsequent chalcogenation reactions of cations R 2P5+ (1 a+, 1 e+) and trication Ph6P73+ (33+) with elemental sulfur (α-S8) or grey selenium (Segrey) yielded a series of unique polyphosphorus-chalcogen cations (4 a+, 4 e+, 5 a+, 62+ and 72+ Copyright
- Holthausen, Michael H.,Hepp, Alexander,Weigand, Jan J.
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supporting information
p. 9895 - 9907
(2013/08/23)
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- Two new phosphorus sulfides
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Jason [1] prepared by the reaction of triphenylantimony sulfide with α-P4S5 and α-P4S7 new phosphorus sulfides. The application of this method on α-P4S4 yielded the main product γ-P4/
- Nowottnick, Heike,Blachnik, Roger
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p. 1966 - 1968
(2008/10/08)
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- A solid state 31P NMR study of the synthesis of phosphorus sulfides from PCI3 and H2S in microporous materials
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The interaction and reaction of PCl3 and PCl3-H2S mixtures with the microporous materials Silicalite, ALPO-5, NaY, NaX, and NaA have been investigated, with the intention of producing phosphorus sulfide clusters in the pores. A rich chemistry was observed and monitored by solid state 31P NMR. The presence of P4S3, α-P4S5, β-P4S6, and P4S7 inside the NaY α-cages was demonstrated, as well as a new species that is possibly a third geometric isomer of P4S4 with C(3v) symmetry. 129Xe NMR showed the exclusion of Xe from the micropores by the phosphorus sulfides. Sulfides lower than P4S7 are small enough that they undergo rapid pseudo-isotropic reorientation inside the NaY α-cage.
- Lee, Garry S. H.,Ratcliffe, Christopher I.,Ripmeester, John A.
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p. 1660 - 1667
(2007/10/03)
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- Products and Mechanisms in the Oxidation of Phosphorus by Sulfur at Low Temperature
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The oxidation of phosphorus by sulfur at low temperatures (8 diradical. This proposal is supported by the observed rate at which the sulfldes are formed and the distribution of the sulfide product stoichiometries. Photoinitiation of this oxidation at 0 °C produces a similar array of sulfldes. The differences in the product distributions between the thermal and photochemical processes facilitate the understanding of the mother-daughter relationships between the products. The effects of oxidation by sulfur and reduction by phosphorus have been determined for several of the known phosphorus sulfides. The characterizations of phosphorus compounds in molten mixtures of phosphorus and sulfur were performed by 31P NMR and Raman spectroscopy directly on the reaction mixtures.
- Jason, Mark E.,Ngo, Toan,Rahman, Shahidur
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p. 2633 - 2640
(2008/10/09)
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- Transfer of Sulfur from Arsenic and Antimony Sulfides to Phosphorus Sulfides. Rational Syntheses of Several Less-Common P4Sn Species
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It has been shown that triphenylarsenic sulfide and triphenylantimony sulfide rapidly transfer sulfur to a number of the known phosphorus sulfides. The reactions are performed at or below room temperature in carbon disulfide solutions. The transfers are neither highly selective nor random, making them useful but not ideal for synthetic purposes. The moderate selectivities of the reactions have been used in the assignment of structures to two new phosphorus sulfides, structures with molecular formulas P4S6 and P4S8. The reactions of P4S3 are unusual in that products with 7-9 sulfur atoms in the molecule are formed competitively with low sulfur products. The usefulness of triphenylantimony sulfide is limited by its tendency to undergo reductive elimination of sulfur. This reduction takes the form of a disproportionation to give triphenylantimony and elemental sulfur and has been shown to occur by a second-order process that appears to involve the formation of disulfur, S2.
- Jason, Mark E.
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p. 2641 - 2646
(2008/10/09)
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- The Molecular Composition of Solidified Phosphorus-Sulfur Melts and the Crystal Structure of β-P4S6
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Phosphorus sulfur melts were annealed for one week at 673 K and then quenched in ice water. The solids were dissolved in CS2 and the concentrations of phosphorus sulfides were determined by (31)P NMR spectroscopy. Samples containing between 44 ant 70 mol% sulfur dissolved completely in CS2. Between 0 and 42 mol% remains an insoluble residue of red phosphorus. Above 72 mol% it consisted of sulfur chains linked by phosphorus atoms. The solutions contained mainly the congruently melting compounds P4S3,P4S7, and P4S10 having maximum concentrations at their stoichiometric c ompositions. Other compounds P4Sn (n=4-9) which decompose on heating, according to the phase diagram, were also found in surprisingly high concentrations. One of these was β-P4S6 which crystallizes in the monoclinic space group P21/C with the lattice parameters a=702.4(2), b=1205.6(2), c=1148.9(6) pm, and β=103.4(2)° Reaction of white phosphorus with sulfur was also investigated. In contrast to the results of previous authors, who described the system P4-S8 below 373 K as eutectic,we found that the elements reacted below this temperature.
- Blachnik, Roger,Peukert, Ulrike,Czediwoda, Anette,Engelen, B.,Boldt, K.
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- The First Hydrides of a Phosphorus Sulfide Cage: Nuclear Magnetic Resonance Evidence for α-Tetraphosphorus Trisulfide Hydride Compounds
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The hydrides α-P4S4(H)R (R = H, I, NMePh or SPh) have been prepared in solution by the reaction of α-P4S3I2 or of the corresponding α-P4S3(I)R with Sn-n-Bu3H, and identified by 31P NMR spectroscopy.The compounds were unstable and not isolated.Ab initio molecular orbital calculations of geometry have been carried out for α-P4S3H2, α-P4S3(NMe2)2 and α-P4S3H(NMe2).
- Tattershall, Bruce W.,Kendall, Nigel L.
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p. 3163 - 3168
(2007/10/02)
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- Multiphase characterization of phosphorus sulfides by multidimensional and MAS-31P NMR spectroscopy. Molecular transformations and exchange pathways at high temperatures
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High-temperature 1D and 2D exchange 31P-NMR spectra of melts of pure and well-defined phosphorus sulfides show that, e.g., β-P4S5 or mixtures of P4S3 and sulfur transform into mixtures of at least eight different P4Sn (n = 3-7) species which are identified and quantified. Transformations and exchange pathways between the different P4Sn species in the melts are revealed by the 2D exchange 31P-NMR spectra at 225-250 °C. Furthermore, the exchange correlations observed from these spectra yield unambiguous assignments of the unknown or earlier incorrectly assigned 31P chemical shifts for β-P4S6, β-P4S5, α-P4S5, and a new P4S6 isomer (α-P4S6). These assignments are extremely valuable for a correct interpretation of the complex solid-state magic angle spinning (MAS)-NMR spectra of phosphorus sulfides. Two polymorphs for both β-P4S5 and α-P4S6 (the predominant species in the β-P4S5 melt and isolated here for the first time) have been isolated and characterized by high-speed 31P MAS-NMR spectroscopy. Molecular distortions, caused by crystal packing and not easily detected by XRD, are observed for all four polymorphs. These distortions cause nonequivalence between phosphorus atoms which are equivalent for the free molecules. Thereby otherwise unobservable isotropic 1J(P,P)'s have been determined from solid-state NMR spectroscopy.
- Bjorholm,Jakobsen
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- New A4B3 Molecules: P3SbS3, P4S2Te and P4STe2
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The new molecules P3SbS3, P4S2Te and P4STe2 were extracted with CS2 from mixtures of S.Sb and P4S3, and P, S and Te samples respectively, which were previously molten and then annealed for several days.In the P3SbS3 molecules the apical phosphorus position of P4S3 is substituted by antimony.In the molecules P4STe2 and P4S2Te one or two of the sulphur bridges are substituted by tellurium.X-ray and 31P NMR data of the compounds are given.
- Baldus, Hans Peter,Blachnik, Roger
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p. 1605 - 1609
(2007/10/02)
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- Concentrations of Isomers of Type PmAs4-mX3 in P4S3-As4S3 and P4Se3-As4Se3 Mixtures
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The reactions of P4S3 with As4S3 and of P4Se3 with As4Se4 in the molten state yields molecules of the type PmAs4-mS3 and PmAs4-mSe3, respectively.A method was developed to separate the different components by the HPLC technique, and to determine their concentrations.The identification of the isomers in the HPLC pattern was achieved with the aid of the LC-MS method.In the selenium system, the distribution of the different species is statistical.In the system P4S3-As4S3, the formation of PAs3S3 with one phosphorus atom in the apical position is favoured. - Keywords: HPLC study of P4S3-As4S3 and P4Se3-As4Se3 mixtures; Constitution isomers of phosphorus arsenic chalcogenides; Equilibrium constants of phosphorus-arsenic exchange reactions
- Baldus, Hans P.,Blachnik, Roger,Schneider, Claudia
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p. 515 - 524
(2007/10/02)
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- STUDY OF THE OPTIMAL PROPERTIES AND PHOTOLUMINESCENCE OF GLASSES IN THE Ge-P-S SYSTEM.
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The structure of GeS//2-P//4S//1//0, GeS//2-P//4S//7, GeS//2-P//4S//3 and the region enriched with sulfur was studied by IR spectroscopy and ESCA. In the IR spectra, absorption bands are due to P equals S, P-S-P, Ge-S, S-S groups. The coexistence of vario
- Mamontova,Mukanov,Vinogradova,Maisashvili,Babievskaya
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p. 635 - 644
(2008/10/08)
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- NITROGEN, PHOSPHORUS, SULFUR - BUILDING STONES OF RINGS AND CAGES
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A review of recent developments in the chemistry of compounds with ring and cage structures made of nitrogen, phosphorus and sulfur atoms is given.Both synthetic and theoretical aspects are considered.
- Fluck, Ekkehard
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- Intermediates in the Photochemical Reaction of Tetraphosphorus Trisulphide with Organic Disulphides; Phosphorus-31 Nuclear Magnetic Resonance Parameters for 2,6-Bis(alkylthio)- and 2,6-Di-iodo-3,5,7-trithia-1,2,4,6-tetraphosphabicycloheptanes and for 3,6-Bis(alkylthio)-2,5,7-tr...
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P4S3 (1) reacts with organic disulphides RSSR under glass-filtered u.v. irradiation to give at first β-P4S3(SR)2 (2) and then α-P4S3(SR)2 (3) (R = Me, Et, or Ph), identified in the product mixtures by their 31P n.m.r. spectra.The identities of β-P4S3(SPh)2 and α-P4S3(SR)2 (R = Et or Ph) have been confirmed by the preparation of products with the same spectra by substitution reactions of β-P4S3I2 or α-P4S3I2 respectively.The 31P n.m.r. spectrum of β-P4S3I2 is reported.
- Tattershall, Bruce W.
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p. 1707 - 1712
(2007/10/02)
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- 31P NMR Spectroscopical Investigations of A4B3 Molecules
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31P NMR data of sixteen molecules in the series P4SxSe3-x (x = 0-3), PyAs4-yS3, and PyAs4-ySe3 (y = 0-4), resp., are given.All molecules have a common structure, in which a basal ring of three Vb-atoms is connected by three chalcogen atom bridges to an apical Vb-atom.The dependence of the data on bond angles and electronegativities is discussed.A linear relationship was found between chemical shift and an angle increment I = 11.3(endo -60 deg) + 5.5(exo -103 deg), which describes the bond angle deviations from the reference molecule P4S3. - Keywords: Tetraphosphorus-trichalcogen Molecules, 31P NMR Spectra, Cage Molecules
- Blachnik, R.,Wickel, U.,Schmitt, P.
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p. 1135 - 1138
(2007/10/02)
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- The P4S3-P4Se3 System
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The system P4S3-P4Se3 was investigated by room temperature and high temperature X-ray techniques, MS- and 31P NMR spectroscopy and differential scanning calorimetry.At room temperature the phase diagram contains three regions of solid solubility, one from P4S3 to ca. 45 mole percent P4Se3 with the α-P4S3 structure, the second from ca. 48 to 60 mole percent P4Se3 of unknown structure, and the third from ca. 65 mole percent P4Se3 to P4Se3 with the α-P4Se3 structure.On heating all these phases transform into a plastic-crystalline modification (β) with complete solid solubility between P4S3 and P4Se3.For β-P4S3 d-values are determined with Cr-Kα1-radiation.At higher temperatures the β-phase transforms into a γ-phase, which was characterized by high-temperature X-ray methods.Mass and 31P NMR spectra reveal a multicomponent system consisting of all possible molecules of the type P4S(x)Se(3-x) (x = 0-3).All samples prepared from the melt are composed of a mixture of all these cage molecules.For P4S3 a new modification is found by the DSC measurements.It can be shown that the enthalpy of melting consists of the β-γ transition enthalpy and the real enthalpy of fusion.Metastable γ-P4S3 can be obtained over a broad temperature region (ca. 440-405 K) on cooling of the melt; it is probably isostructural with γ-P4Se3.For the α-β and β-γ transitions several kinds of hysteresis effects are described. - Key words: Phosphorus-Sulfides-Selenides, Cage Molecules, Plastic Crystals, Phase Diagram, Phase Transition in P4S3
- Blachnic, Roger,Wickel, Ulrike
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p. 1507 - 1513
(2007/10/02)
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- Cage Compounds in the System P4S3-As4S3
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Mixtures of P4S3 and As4S3 were investigated.The system reveals a broad metastable region of solid solubility.At the composition PAs3S3 new structures are obtainable after various thermal treatments.In the mixtures six different cage molecules (P4-xAsxS3 (x=1-3)) were found.PAs3S3 is the most stable of the mixed cages.At higher temperature a plastic-crystalline modification, at the composition PAs3S3 two further high temperature modifications are observed.NMR and mass spectra, and d-values of the modifications are reported, and the high temperature behaviour of all mixed cages is described. - Keywords: Phosphorus Arsenic Sulfides, Cage Molecules, Plastic Crystals, Phase Diagrams, Chalcogenides
- Blachnik, R.,Hoppe, A.,Rabe, U.,Wickel, U.
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p. 1493 - 1499
(2007/10/02)
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