31P-KERNRESONANZUNTERSUCHUNGEN VON P4S9 UND P4S10

Abstract

The preparation of P₄P₉ from P₄S₃ and sulfur in decalin is described. The ³¹P nmr spectra of P₄S₉ and P₄S₁₀ are presented and discussed.

Die Darstellung von P₄S₃ aus P₄S₃ und Schwefel in Dekalin wird beschrieben. Die ³¹P-NMR-Spektren von P₄S₉ und P₄S₁₀ sind angegeben und interpretiert.     

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.     

Die Molekulare Zusammensetzung von erstarrten Phosphor-Schwefel-Schmelzen und die Kristallstruktur von β-P4S6

The Molecular Composition of Solidified Phosphorus-Sulfur Melts and the Crystal Structure of β-P₄S₆ 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 ³¹P NMR spectroscopy. Samples containing between 44 and 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 compositions. Other compounds P₄S_n (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 = 1 205.6(2), c = 1 148.9(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.     

STEREOSPECIFIC FORMATION OF A 1,2λ3 -AZAPHOSPETANE IN THE THERMOLYSIS OF BIS[BIS(DIISOPROPYLAMINO)PHOSPHANYL] DIAZOMETHANE

Abstract

Heating of bis[bis(diisopropylamino)phosphanyl]diazomethane 7. in refluxing benzene for 48 hours, quantitatively led to the corresponding 1.2λ³-azaphosphetane 9 as only one diastereoisomer. This result is explained in terms of carbene insertion into a methin-CH bond of an isopropyl substituent. The regiospecificity and the stereospecificity of the ring closure is discussed. Treatment of 9 with elemental sulfur afforded the corresponding 1.2.2λ³-azathiophosphetane 10 which has been characterized b X ray crystallo raphy: C₂₅H₅₆N₄P₂S₂, space group P2(l)/n, a = 13.628 (3) Å, 6 = 19.369 (5) Å, c 112.485 (4) Å, V = 3073 (3) ų.     

Crystal Structure and Vibrational Spectrum of Dipotassium Manganese(II) Hexathiodiphosphate(IV), K2Mn[P2S6]

K₂Mn[P₂S₆] was synthesized from the elements in sealed quartz ampoules at 1 173 K. The compound forms transparent light brown crystals, stable against air and moisture. The crystal structure (monoclinic; space group P2₁/n, No. 14; a = 6.1966(9), b = 12.133(2), c = 7.424(1) Å, β = 101.52(1)°, Z = 2; Pearson code mP22) consists of columns of face-sharing S₆ polyhedra (distorted octahedra and trigonal antiprisms) parallel to the a axis, interconnected by inserted K⁺ (CN 10; d(K? S) = 3.23–3.92 Å). The S₆ polyhedra of the columns are centered alternately by Mn (in octahedra with d?(Mn? S) = 2.647 Å) and P₂ pairs (in trigonal antiprisms) which are inclined to the a axis by 73.1°. The bond lengths in the resulting hexathiodiphosphate(IV) anions, [P₂S₆]^4?, with approximate 3 2/m–D_3d symmetry, are d(P? P) = 2.211 Å and d(P? S) = 2.018 Å. K₂Mn[P₂S₆] is isotypic to K₂Fe[P₂S₆], being the second member of this structure type. The internal modes of the observed Raman and FIR/IR spectra of K₂Mn[P₂S₆] are in accord with the factor group analysis, and the fundamentals are assigned on the basis of [P₂S₆]^4? units, taking into account the deviation of the D_3d symmetry.     

Thermal Behavior of Pyridinium Salt of 2,4-Dimer-Capto-2,4-Dithioxo-1,3-Bis(Trimethylsilyl)-1,3-Diaza-2λ5, 4λ5-Diphosphetidine

Abstract

The reaction of P₄S₁₀with PSCL₃ in pyridine leads to Py.PS₂Cl (1). This substance yields by the reaction with hexamethyldiailazane in molar ratio 1:l a new subatance that was identified as pyridiniwn salt of 2,4-dimercapto-2,4-dithioxo-1,3-bis(trimethylsilyl)-1,3-diaza-2λ⁵,4λ⁵-diphosphetidine (PYH)₂/S₂P(NSiMe₃)₂PS₂/ (I). (2).     

On the Preparation and Properties of a Thiodi-Phosphorus (IV)-Acid Betaine

Abstract

On heating phosphorusi(v) sulfide in anhydrous pyridine the pentathiodiphosphorus(V) acid-P,P′-bis(pyrididium betaine), (C₅H₅N)₂P₂S_B (1), is formed (1,2). In 1 the P atoms are linked via an S atom. The nucleophilic degradation of the sultid P₄S_T by pyridine yields the new tetrathiodiphosphorus(IV) acid-P,P′-bis(pyrididium betaine), (C₅H₅N)₂P₂S₄ (2, which contains a direct P-P bond. 2 is already formed at room temperature on shaking ot P₄S_T with anhydrous pyridine for several days, resulting as a microcrystalline yellow solid in almost 50% yield. As has been proven by means of ³¹P NMH spectroscopy, P₄S_a is a further product of this reaction.     

Molecular dynamics in the nematic,SA and SC phases of 8S5 and 9S5 as studied by dielectric methods

Abstract

Two experimental techniques—time domain spectroscopy (TDS) and a steady state frequency method—have been used to study dielectric spectra for the isotropic, nematic, S_A, S_C and S_Y phases of two thioesters (4-n-pentylphenyl-4′-n-octyloxy-and 4′-n-nonyloxythiobenzoates (C _n H_2n+1 O?C₆ H₄?COS?C₆H₄?C₅H₁₁, where n = 8 and n = 9) known as 8S5 and 9S5, in the frequency range from 10 Hz to 10 GHz. In the case of 8S5 a deuteriated sample (8S5-d ₂₈) has been used to study relaxation processes in the nematic and smectic phases.     

Synthesis,crystal structure,magnetism and vibrational spectrum of Dipotassium Iron(II) Hexathiodiphosphate(IV), K2Fe[P2S6]

K₂Fe[P₂S₆] was synthesized from the elements at 1173 K in sealed quartz tubes. The compound forms transparent orange crystals, stable against air and moisture. K₂Fe[P₂S₆] crystallizes in the monoclinic system, space group P2₁/n (No. 14), with cell dimensions (T = 298.5 K) a = 6.0622(4), b = 12.172(1) and c = 7.3787(8) Å, β = 101.113(7)°, Z = 2. The novel structure type (mP22) is characterized by columns of alternating face-sharing S₆ octahedra and trigonal antiprisms (both distorted) parallel to the a axis, which are interconnected by inserted K⁺ (CN 10; {2,6,2}-polyhedra; d(K? S) = 3.231 ? 3.845 Å). The S₆ polyhedra of the columns are centered alternately by Fe (d?(Fe? S) = 2.577 Å) and P₂ pairs which are inclined to the a axis by 73.4°. The bond lengths in the hexathiodiphosphate(IV) anions, [P₂S₆]^4?, with approximate 3 2/m – D_3d symmetry, are d?(P? P) = 2.20 and d?(P? S) = 2.02 Å. The compound is paramagnetic above T_N = 28 K with μ = 4.69 B.M. and orders antiferromagnetically below T_N. The internal modes of the observed Raman and FIR spectra of K₂Fe[P₂S₆] are in accord with the factor group analysis, and the spectra are assigned on the basis of [P₂S₆]^4? units, taking into account the deviation from D_3d symmetry.     

Beiträge zur Chemie von Phosphorverbindungen mit Adamantanstruktur. XI. Über Darstellung und Eigenschaften von Phosphoroxidsulfiden der allgemeinen Formel P4O10−nSn (n = 2−9)

Contributions to the Chemistry of Phosphorus Compounds with Adamantane-like Structure. XI. Preparation and Properties of Phosphorus Oxide Sulfides of the General Formula P₄S_10?n S_n (n = 2?9) The reaction of P₄O₁₀ with P₄S₁₀ yields a mixture of phosphorus oxide sulfides of the general formula P₄O_10?nS_n. Depending on the molar ratio P₄O₁₀: P₄S₁₀ in the starting product different amounts of the individual phosphorus oxide sulfides occuring in this reorganization product are formed. Besides the well-known P₄O₆S₄ the compounds P₄O₇S₃, P₄O₅S₅, P₄O₄S₆, P₄O₃S₇, P₄O₂S₈, and P₄OS₉ occuring for the first time were obtained by fractional distillation or crystallization. The compound P₄O₈S₂ was identified by N.M.R. spectroscopy.     

2, 4-bis(4-methoxyphenyl)-1, 3, 2, 4-dithiadiphosphetane 2, 4-disulfide,lr, as a new activation reagent in preparation of peptides,amides and esters

Abstract

2, 4-Bis(4-methoxyphenyl)-1, 3, 2, 4-dithiadiphosphetane 2, 4-disulfide, LR, is easily prepared by refluxing P₄S₁₀ in anisole for two hours produces the title compound in high yield.     

Drei Alkalimetall‐Erbium‐Thiophosphate: Von der Schichtstruktur bei KEr[P2S7] zur dreidimensionalen Vernetzung in NaEr[P2S6] und Cs3Er5[PS4]6

Three Alkali‐Metal Erbium Thiophosphates: From the Layered Structure of KEr[P₂S₇] to the Three‐Dimensional Cross‐Linkage in NaEr[P₂S₆] and Cs₃Er₅[PS₄]₆ The three alkali‐metal erbium thiophosphates NaEr[P₂S₆], KEr[P₂S₇], and Cs₃Er₅[PS₄] show a small selection of the broad variety of thiophosphate units: from ortho‐thiophosphate [PS₄]^3? and pyro‐thiophosphate [S₃P–S–PS₃]^4? with phosphorus in the oxidation state +V to the [S₃P–PS₃]^3? anion with a phosphorus‐phosphorus bond (d(P–P) = 221 pm) and tetravalent phosphorus. In spite of all differences, a whole string of structural communities can be shown, in particular for coordination and three‐dimensional linkage as well as for the phosphorus‐sulfur distances (d(P–S) = 200 – 213 pm). So all three compounds exhibit eightfold coordinated Er³⁺ cations and comparably high‐coordinated alkali‐metal cations (CN(Na⁺) = 8, CN(K⁺) = 9+1, and CN(Cs⁺) ≈ 10). NaEr[P₂S₆] crystallizes triclinically ( ; a = 685.72(5), b = 707.86(5), c = 910.98(7) pm, α = 87.423(4), β = 87.635(4), γ = 88.157(4)°; Z = 2) in the shape of rods, as well as monoclinic KEr[P₂S₇] (P2₁/c; a = 950.48(7), b = 1223.06(9), c = 894.21(6) pm, β = 90.132(4)°; Z = 4). The crystal structure of Cs₃Er₅[PS₄] can also be described monoclinically (C2/c; a = 1597.74(11), b = 1295.03(9), c = 2065.26(15) pm, β = 103.278(4)°; Z = 4), but it emerges as irregular bricks. All crystals show the common pale pink colour typical for transparent erbium(III) compounds.     

Phase transitions in ferroelectric liquid crystals in a restricted geometry

Abstract

Using a wedge type cell, we have studied the S_A–S*_c, S*_c–S_c and S_A–S_c phase transition lines in the ferroelectric liquid crystals 4-(2-methylbutyl)phenyl 4′-n-octylbiphenyl-4-carboxylate (CE-8) and 2-methylbutyl 4-(4-decyloxy-benzylidene)aminocinnamate (DOBAMBC) as a function of cell thickness in the planar geometry. The phase diagram is similar to the one observed using an external magnetic field. A surface induced re-entrant-like phenomenon is also observed. The experimental results are compared with the predictions of a Landau model with surface anchoring and a qualitative agreement was found. The results show that whereas disclination lines are not important for the S_A–S*_c and S_A–S_c transition lines, these defects have to be taken into account when evaluating the S*_c→S_c transition line. The form of the phase diagram has some important implications for the performance of surface stabilized ferroelectric liquid crystal cells used in electrooptic devices.     

Darstellung von Schwermetallchalkogenid-Einkristallen durch chemischen Transport mit Aluminiumchlorid

Zusammenfassung Durch chemischen Transport mit wasseerfr. AlCl₃ als Transportmittel konnten folgende Schwermetallsulfide und-selenide in Form von Einkristallen erhalten werden: Cr₂S₃, Cr₃S₄, Cr₅S₆, Cr₇S₈, CrS, Cr₂Se₃, Cr₇Se₈, CoS₂, CoS, (Co), NiS₂, NiS, ZnCr₂S₄, CdCr₂S₄, MnCr₂S₄, ZnCr₂Se₄, CdCr₂Se₄, HgCr₂Se₄, CuCr₂Se₄, NiCr₂S₄, Ni_0,95Cr_0,05S, Ni_0,83Cr_0,17S, Ni_0,75Cr_0,25S. Der Mechanismus des Transports mit AlCl₃ und die Darstellung größerer Einkristalle werden diskutiert.

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Growing of chalcogenide single crystals by chemical transport with aluminium chloride

Single crystals of the following compounds have been grown by chemical transport with anhydrous aluminium chloride as transporting agent: Cr₂S₃, Cr₃S₄, Cr₅S₆, Cr₇S₈, CrS, Cr₂Se₃, Cr₇Se₈, CoS₂, CoS, (Co), NiS₂, NiS, ZnCr₂S₄, CdCr₂S₄, MnCr₂S₄, ZnCr₂Se₄, CdCr₂Se₄, HgCr₂Se₄, CuCr₂Se₄, NiCr₂S₄, Ni_0,95Cr_0,05S, Ni_0,83Cr_0,17S, Ni_0,75Cr_0,25S. The growing of larger crystals and the mechanism of the transport with AlCl₃ are discussed.

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Cs. Lovász, Teil der Dissertation, Universität Köln 1969.

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K.-H. Bertram, Teil der diplomarbeit, Universität Köln 1970.     

α,ω-Bis(Dialkylthiophosphoryl)Sulfanes-Products of the Alcoholysis of Sulfur-Rich Phosphorus Sulfides

Abstract

The high solubility of sulfur-rich phosphorus sulfides in CS₂-especially in the range S:P=2.7 to 4-is the motive for new investigations on this system. DEMARCQ¹ suppsed the existence of “molecular products”, but he coulds not prove it by spectroscopic and chemical methods. As we have found the formation of α, ω-bis (fluorodithicphosphoryl) oliqosulfanes at the nucleophilic degradation of phosphorus sulfides with fluorides gives no proof for the existence of oligosulfane bridges in the sulfur-rich phosphorus sulfides. On the reaction of P₄S₁₀, elementary sulfur and alka-lifluorides the same products are formed. Sulfur-rich phosphorus sulfides and alcohols also react to mixtures of α,ω-bis (dialkylthiophosphoryl)sulfanes. But these compounds are not obtained by the reaction of P₄S₁₀ and sulfur with alcohols.     

Phosphorus Containing Achiral Reagents for the Determination of Enantiomeric Composition of Chiral Alcohols

Abstract

It is shown that P₄S₁₀ and (R₂N)3P can be used as achiral derivatising reagents for the determination of enantiomeric excess (ee) of chiral alcohols R*OH.     

Coordination properties of the multifunctional S,N,S zwitterionic ligand EtNHC(S)Ph2PNPPh2C(S)NEt

The reaction of trialkylphoshanes and amino-phosphanes with isothiocyanates yields adducts containing the zwitterionic thioamidyl-phosphonium P⁺C(S)N^? functional group. Ligands containing this group were not previously studied, probably due to their instability towards dissociation, in the presence of metal species able to coordinate the P atom. The ligand EtNHC(S)Ph₂PNPPh₂C(S)NEt (HEtSNS) was obtained by reaction of Ph₂PNHPPh₂ with ethylisothiocyanate and proved to be very versatile: it can be protonated giving cation H₂EtSNS⁺ and deprotonated forming the dianion–cation EtSNS^?. HEtSNS and its derivatives behave as ligands showing five possible coordination fashions, S,N,S tridentate and S,S-bidentate (with a bite-angle varying from 180° to 90°), S-monodentate, S,S bridging and N,N,N interaction. Here we describe the coordination chemistry of HEtSNS, in particular towards Rh, Cu, Ag and Au, and some properties of its complexes which are still the only examples containing the P⁺C(S)N^? zwitterionic group.     

NOVEL MOLECULAR PHOSPHORUS SULFIDES WITH S/P HIGHER THAN 2.5. I. GENESIS AND CHARACTERIZATION BY PHYSICAL AND CHEMICAL METHODS

Abstract

PS _x alloys (x = 2.75 to 71.5), prepared by heating P₄S₁₀ with excess sulfur at 300–312°C, have been extensively extracted by carbon disulfide at room temperature. The solutions have been shown by ³¹P NMR to contain, besides P₄S₁₀ and P₄S₉, a number of novel species, hereafter called soluble Phosphorus Poly-(or Per-)sulfides (PPS). Electronic and IR spectra are reported. All attempts at separating pure individual PPS have failed. Soluble PPS are metastable, with a definite tendency to polymerize. They are selectively desulfurized by Ph₃P. They decolorize Diphenylpicrylhydrazyl instantly. NMR monitored experiments led to a classification of soluble PPS according to their rate of hydrolysis.     

Kristallstruktur und Eigenschaften von Calcium- und Strontiumhexathiodiphosphat(IV), Ca2P2S6 und Sr2P2S6, mit einem Beitrag zu Ca5P8 und Pb2P2S6

Crystal Structure and Properties of Calcium and Strontium Hexathiodiphosphate(IV), Ca₂P₂S₆ and Sr₂P₂S₆, with a Contribution on Ca₅P₈ and Pb₂P₂S₆ Ca₂P₂S₆ and Sr₂P₂S₆ were prepared from metal and a mixture of red phosphorus and sulfur (molar ratio M:P:S = 1:1:3) in 2 corundum crucibles inserted in quartz ampullae under vacuum (20 d 900°C). The compounds were obtained as colourless, crystalline powders containing single crystals. They crystallize in the Sn₂P₂S₆ (high temperature form) type structure (P2₁/c, Z = 2): Ca₂P₂S₆ a = 653.2(2)pm, b = 728.1(2)pm, c = 1110.1(4)pm, β = 124.00(4)°, d = 2.50(2); Sr₂P₂S₆ a = 664.3(2)pm, b = 755.7(3)pm, c = 1139.7(3)pm, β = 124.07(2)°, d = 2.97(2). The anions P₂S have staggered confirmation and are arranged with the motif of a cubic close-packing. Sr²⁺ is coordinated by 8S which form a twofold face-capped trigonal prism and belong to 4P₂S. Structure calculations clearly show that Pb₂P₂S₆ also crystallizes in P2₁/c and not in Pc [1]. Also, Raman- and IR-spectra of Ca₅P₈ were recorded at 20°C. The stretching vibrations of P were assigned in analogy to those of P₂S in alkaline earth hexathiodiphosphates(IV). The range of their frequencies (480 to 340 cm^?1) is essentially smaller and shifted to smaller values compared with P₂S in Ca₂P₂S₆ and Sr₂P₂S₆ (620 to 390 cm^?1). The symmetry of P is not D_3d but C_2h as in the case of P₂S.     

New Reactions of Olefins with Tetraphosphorus Decasulfide,Thiophosphoryl Trichloride,and Phosphorus Trichloride

Abstract

In contrast to difficultly characterizable products of olefins with P₄S₁₀ alone, the reactions of olefins with P₄S₁₀ in the presence of PSCI₃ (and in some cases, PCl₃) afforded distillable products amenable to characterization. Ethylene with P₄S₁₀, PSCl₃, and PCl₃ gave 1,2-ethanediylbis (phosphonothioic dichloride) in good yield. Propylene with P₄S₁₀ and PSCl₃ afforded several open-chain phosphonothioic chlorides and at higher temperatures 2-chloro-1,2-thiaphospholane 2-sulfide. 1- or 2-Butene yielded the 5-methyl homolog. Cyclohexene yielded 7-chloro-6-thia-7-phosphabicyclo [3.2.1] octane 7-sulfide and 4-methylcyclohexene yielded the 5-methyl homolog. Norbornene gave stereoisomeric 3-chloro-2-thia-3-phosphatricyclo [4.3.0.0^4,8] nonane 3-sulfides. Norbornadiene gave 3-chloro-2-thia-3-phosphatricyclo [4.3.0.0^4,8] non-6-ene 3-sulfide. Camphene reacted with P₄S₁₀ and PSCl₃ in good yield at ambient pressure and moderate heating to produce a characteristic Wagner-Meerwein rearrangement product, 3-chloro-3-phospha-4-thia-10, 10-dimethyltricyclo-[5.2.1.0^1,5] decane 3-sulfide. Butadienes with P₄S₁₀ and PSCl₃ afforded Diels-Alder-like 2-chloro-3,6-dihydro-2H-1, 2-thiaphosphorins. These products were characterized by nmr and, in some instances, by hydrolysis to characterizable products. The products are generally consistent with electrophilic mechanisms.