Derivate von arsensubstituierten Phosphorchalkogeniden

Derivatives of Arsenic Substituted Phosphorus Chalcogenides α-AsP₃S₃I₂, α-AsP₃Se₃I₂, and three isomers of β-AsP₃S₃I₂ were observed besides several phosphorus sulfides by ³¹P NMR spectroscopy after the reaction of As_nP_4–nE₃ (E ? S; Se; n = 0–4) with I₂ in the melt or with I₂, PI₃, and N-iodosuccinimid in CS₂ solutions. The reaction of As_nP_4–nS₃ with CHI₃ in CS₂ solution yielded two isomers of β-AsP₃S₃(CHI₂)I.     

Zur Reaktion von Phosphor(Arsen)-chalkogeniden mit Phosphor(Arsen)-triiodid

Reactions of Phosphorus(Arsenic)chalcogenides with Phosphorus(Arsenic)triiodide The specific heats and enthalpies of melting of the tetraphosphorustrithio(seleno)-diiodides have been determined. For the preparation of β-P₄S₃I₂ a new mthod by reacting P₄S₃ with PI₃ in CS₂ solution was found. Experiments to prepare compounds of the type As₄S₃I₂ by the classical methods for the preparation of the resp. phosphorus compounds failed. The reaction of As₄S₃ with AsI₃ leads to the formation of As₄S₄. The other sulphides of the As? S system As₂S₃ and As₄S₄ react with AsI₃ to AsSI, however, in the reaction of As₄S₄ the addition of S is necessary.     

Die elektrochemische Reduktion von CSSe und CSe2 in Dimethylformamid: Heterocyclische 1,2-Dichalkogenolate und ihre Koordinationschemie

Electrochemical Reduction of CSSe and CSe₂ in Dimethylformamide: Heterocyclic 1,2-Dichalcogenolates and their Coordination Chemistry Starting from carbon diselenide or carbon selenidesulfide the electrochemical preparation (electrosynthesis) of heterocyclic dichalcogenolates C₃X₅^2? (X = Se: dsis; X = S/Se: C₃S_xSe_y^2?) is outlined. The 1,2-dichalcogenolate compounds were isolated and characterized as dibenzoyl derivatives. Bis- or tris-chelates of general type A_m[M(C₃X₅)_n] (with A = Bu₄N⁺, Ph₄As⁺; M = Zn^II, Pt^II, Pd^II, Ni^III, Cu^III, Au^III, In^III; X = Se, S/Se; m = 1, 2, 3; n = 2, 3, respectively) are available directly from methanolic solutions of the dibenzoylates after hydrolytic cleavage of the latter with sodium methanolate. In addition bis-chelates Bu₄N[Ni(C₃X₅)₂] (X = Se, S/Se) have been characterized by cyclovoltammetry and epr spectroscopy and compared with the corresponding all-sulfur ligand compound Bu₄N[Ni(dmit)₂] (X = S). Arguments are given for the fact that the allselenium ligand dsis (X = Se) yields the Cu^III or Ni^III chelate at once whereas with dmit using identical conditions the metal(II) compounds are formed.     

Die Kristallstruktur von K2S3 und K2Se3

The Crystal Structure of K₂S₃ and K₂Se₃ Well formed crystals of K₂S₃ and K₂Se₃ were obtained by reaction of the elements in liquid ammonia at 500 bar and 150°C. The substances are both orthorhombic, space group Cmc2₁. Cell constants are: The structure contains S₃^2?(Se₃^2?) polyanions, with S? S? S(Se? Se? Se) angles of 105.4(102.5)°. The S? S(Se? Se) distance is 2.083(2.383) Å.     

Über die Umsetzung von P4E3I2 (E = S,Se) mit einigen Carbonsäuren und Dithiocarbonsäuren

On the Reaction of P₄E₃I₂ (E = S, Se) with some Carboxylic Acids and Dithiocarbamic Acids By the reaction of α-P₄E₃I₂ (E = S, Se) with carboxylic acids, dithiobenzoic acid or dithiocarbamic acids in the presence of triethylamin or with (C₆H₅)₃SnR, or of β-P₄E₃I₂ with tin-organic compounds α-P₄E₃(I)R, α(β)-P₄E₃R₂ [R = ? OC(O)C₆H₅, ? OC(O)CH₃, ? SC(S)NC₅H₁₀, ? SC(S)N(C₂H₅)₂], α-P₄S₃(I)SC(S)C₆H₅, α-P₄S₃(SC(S)C₆H₅)₂ and β-P₄E₃(I)R (R = ? OC(O)C₆H₅, ? OC(O)CH₃) were prepared in solution and identified by ³¹P NMR spectroscopy. In addition α-P₄S₃(NC₅H₁₀)(SC(S)NC₅H₁₀) was detected. The β-isomers could be obtained also with lesser yields by the reaction with the dithiocarbamic acids, too. The substitution of the second iodine ligand in β-P₄E₃I₂ resulted mainly in β-P₄S₃(R_exo)₂ and by inversion of the configuration at a phosphorus atom, in β-P₄E₃R_exoR_endo. α-P₄S₃I₂ reacted with methanol in CS₂ to α-P₄S₃(OCH₃)(SC(S)OCH₃) and α-P₄S₃(SC(S)OCH₃)₂. The ³¹P NMR data of the compounds are discussed. The ³¹P NMR spectra of the α(β)-P₄E₃ dithiocarbamates indicate dynamic processes in the solution, e. g. α-P₄S₃(I)(SC(S)NR₂) showed an intramolecular conversion, due to the anisobidentate dithiocarbamate ligand. This behaviour had not previously been noticed for compounds with a P₄S₃-skeleton.     

Darstellung und Kristallstruktur einer neuen isomeren Form von As4S4

Preparation and Crystal Structure of a New Isomeric Form of As₄S₄ As₄S₄(II) was prepared by melting of the pure elements As and S in the atomic ratio 1:1 at the temperature range 500°–600°C and a quickly cooling to the room temperature. Yellow-orange coloured and very thin platy single crystals were recrystallized from a CS₂ solution. The crystal parameters are: a = 11.193, b = 9.994, c = 7.153 Å and β = 92.8°. The space group in P2₁/n (No. 14). The molecule can be principally deduced from the As₄-tetraedron. By the connection of the folded plane SAs₃ to the platy pyramide S₃As the cage structure of the As₄S₄(II) molecule will be built.     

Doping Sumanene with Both Chalcogens and Phosphorus(V): One‐Step Synthesis,Coordination, and Selective Response Toward AgI

Heterasumanenes 4 – 6 containing chalcogen (S, Se, and Te) and phosphorus atoms have been synthesized in a one‐pot reaction from trichalcogenasumanenes 1 – 3 by replacing one chalcogen atom with a P=S unit. The P=S unit makes 4 – 6 almost planar and shrinks the HOMO–LUMO gap as compared to 1 – 3 . The bonding between Ag⁺ and S atom on P=S brings about a distinct change to the optical properties of 4 – 6 ; 4 in particular shows a selective fluorescence response toward Ag⁺ with LOD of 0.21 μm . Compounds 4 – 6 form complexes with AgNO₃ to be ( 4 )₂?AgNO₃, ( 5 )₂?AgNO₃, and ( 6 )₂?(AgNO₃)₃. In complexes, the coordination between Ag⁺ and P=S is observed, which leads to shrinkage of C?P and C?X (X=S, Se, Te) bond lengths. As a result, 4 , 5 , and 6 are all bowl‐shaped in complexes with bowl‐depths reaching to 0.66 Å, 0.42 Å, and 0.40 Å, respectively. There are Ag?Te dative bonds between Ag⁺ and Te atom on telluorophene in ( 6 )₂?(AgNO₃)₃.     

Reaktionen von Oxiden der Elemente der V. Hauptgruppe mit Trithiazylchlorid Kristallstruktur von (S5N5)4[As8Cl28] · 2 S4N4

Reactions of Element Oxides of the Fifth Main Group with Trithiazyl Chloride. Crystal Structure of (S₅N₅)₄[As₈Cl₂₈] · 2 S₄N₄ Whereas P₄O₁₀ does not react with (NSCl)₃, the oxides As₂O₃, Sb₂O₃, and Bi₂O₃ react under formation of (S₅N₅)₄[As₈Cl₂₈] · 2 S₄N₄, S₅N₅[SbCl₆] and a mixture of S₄N₅[BiCl₄] and S₄N₄Cl[BiCl₄], respectively. The products were characterized by their IR spectra. The crystal structure of (S₅N₅)₄[As₈Cl₂₈] · 2 S₄N₄ was determined by means of X-ray diffraction (1168 independent observed reflexions, R = 0.059). Crystal data: tetragonal, space group P4 2₁c, Z = 2, a = 1596.6, c = 1520.1 pm. The compound consists of planar S₅N₅^⊕ cations, octameric anions [As₈Cl₂₈]^4? and S₄N₄ molecules. The S₅N₅^⊕ ions and the S₄N₄ molecules show positional disorder, which very probably is of dynamical type for the S₅N₅^⊕ ion. The [As₈Cl₂₈]^4? ions can be described as a (so far unknown) [As₄Cl₁₆]^4? ion with cubane-like structure (As? Cl bridging distances between 286 and 305 pm) to which four AsCl₃ molecules are attached via chloro bridges with As? Cl bond lengths between 314 and 328 pm.     

Phasenbeziehungen im System Se?Br und die Kristallstrukturen des dimorphen SeBr4

Phase Relations and Crystal Structures in the System Se? Br The system Se? Br contains two intermediate phases with congruent melting behaviour: α-SeBr (+5°C) and α-SeBr₄ (+123°C). β-SeBr and β-SeBr₄ are metastable with respect to the phase diagram and are irreversibly transformed to the α-modifications by annealing. Phase relations in the Se? Br system are discussed in detail. Single crystals of α- and β-SeBr₄ are obtained by vapour phase transport. β-SeBr₄ is monoclinic, space group C2/c, z = 16, a = 17.02, b = 10.39, c = 15.49 Å, β = 117°, and is an isotype of TeCl₄. α-SeBr₄ is trigonal, space group P31c, z = 16, with a = 10.200(7), c = 30.351(18) Å. In both modifications tetrameric cubane-like molecules [SeBr₄]₄ are present, but with different spatial arrangement. The crystal structure of α-SeBr₄ is discussed in terms of packing aspects.     

Doping Sumanene with Both Chalcogens and Phosphorus(V): One‐Step Synthesis,Coordination, and Selective Response Toward AgI

Heterasumanenes 4 – 6 containing chalcogen (S, Se, and Te) and phosphorus atoms have been synthesized in a one‐pot reaction from trichalcogenasumanenes 1 – 3 by replacing one chalcogen atom with a P=S unit. The P=S unit makes 4 – 6 almost planar and shrinks the HOMO–LUMO gap as compared to 1 – 3 . The bonding between Ag⁺ and S atom on P=S brings about a distinct change to the optical properties of 4 – 6 ; 4 in particular shows a selective fluorescence response toward Ag⁺ with LOD of 0.21 μm . Compounds 4 – 6 form complexes with AgNO₃ to be ( 4 )₂?AgNO₃, ( 5 )₂?AgNO₃, and ( 6 )₂?(AgNO₃)₃. In complexes, the coordination between Ag⁺ and P=S is observed, which leads to shrinkage of C?P and C?X (X=S, Se, Te) bond lengths. As a result, 4 , 5 , and 6 are all bowl‐shaped in complexes with bowl‐depths reaching to 0.66 Å, 0.42 Å, and 0.40 Å, respectively. There are Ag?Te dative bonds between Ag⁺ and Te atom on telluorophene in ( 6 )₂?(AgNO₃)₃.     

Laser ablation of ternary As‐S‐Se glasses and time‐of‐flight mass spectrometric study

Ternary chalcogenide As‐S‐Se glasses, important for optics, computers, material science and technological applications, are often made by pulsed laser deposition (PLD) technology but the plasma composition formed during the process is mostly unknown. Therefore, the formation of clusters in a plasma plume from different glasses was followed by laser desorption ionization (LDI) or laser ablation (LA) time‐of‐flight mass spectrometry (TOF MS) in positive and negative ion modes. The LA of glasses of different composition leads to the formation of a number of binary As_pS_q, As_pSe_r and ternary As_pS_qSe_r singly charged clusters. Series of clusters with the ratio As:chalcogen = 3:3 (As₃S, As₃S₂Se⁺, As₃SSe), 3:4 (As₃S, As₃S₃Se⁺, As₃S₂Se, As₃SSe, As₃Se), 3:1 (As₃S⁺, As₃Se⁺), and 3:2 (As₃S, As₃SSe⁺, As₃Se), formed from both bulk and PLD‐deposited nano‐layer glass, were detected. The stoichiometry of the As_pS_qSe_r clusters was determined via isotopic envelope analysis and computer modeling. The structure of the clusters is discussed. Copyright © 2009 John Wiley & Sons, Ltd.     

Phase equilibrium in the As2S3-TlSe system

The interaction between the components of the As₂S₃-TlSe system has been studied using diffeential thermal analysis, powder X-ray diffraction, microstructure examination, and microhardness and density measurements. Two new quaternary compounds, TlAs₂S₃Se and Tl₃As₂S₃Se₃, are formed in the system. Both compounds may be prepared in a glassy state. They melt congruently at 350 and 280°C, respectively. The section As₂S₃-TlSe is a stable diagonal of the ternary reciprocal system As,Tl ‖ S, Se. The As₂S₃-base solid solution extends to 1.5 mol % TlSe. The extent of the TlSe-base solution is 5.2 mol % As₂S₃. Under slow cooling, the glass field in the system extends to 85 mol % TlSe; when the system is quenched to liquid nitrogen, the extent of the glass field is 100 mol % TlSe.     

Neue Moleküle A4B3 im System P4Se3–As4Se3

Novel A₄B₃ Molecules in the System P₄Se₃–As₄Se₃ By means of ³¹P-NMR and masspectroscopic measurements in the system P₄Se₃–As₄Se₃ was shown that in the melt and vapour phase at all compositions molecules of the type P_{4 ? n}As_nSe₃ are formed. A separation was possible by liquid chromatography (RP 18-column). The concentration distribution of the different species is nearly statistical. In the solid state at ambient temperature regions of solid solubility with α-P₄Se₃, α⁺-phase, α-P₄S₃ and α-As₄Se₃ structure were observed. P₃AsSe₃ could be transformed into a plastically-crystalline phase with β-P₄S₃ structure. At higher temperatures the phase decomposes slowly. The thermal behaviour of PAs₃Se₃ is strongly influenced by the heating rate. Using low heating rates it decomposes into an amorphous phase, by fast heating a transformation into a metastable plastically-crystalline modification was achieved. During long extraction with CS₂ molecules P_{4 ? n}As_nS_{3 ? m}Se_m are formed by an exchange reaction. They can also be prepared by melting the proper amounts of the elements.     

Schwingungsspektren von As4S4 und As4Se4

Vibrational Spectra of As₄S₄ and As₄Se₄ The vibrational spectra of solid α- and β-As₄S₄ and the Raman spectrum of molten As₄S₄ have been recorded. The assignments of the frequencies are proposed mainly based on polarization data. The Raman melt spectra suggest that As₄S₄ molecules (symmetry D_2d) are retained in the molten state. A partial decomposition of the melt by prolonged laser irradiation was observed. The Raman spectrum of solid As₄Se₄ is presented and the frequencies are tentatively assigned to an As₄Se₄ molecule of the cradle type, possessing D_2d symmetry.     

Solid State Chemistry of A4B3−Molecules

Abstract

The system P₄S₃?P₄Se₃?As₄S₃?As₄Se₃ was investigated by thermal and X-ray methods. Five regions of solid solubility with different crystal structures were found. All transform at higher temperatures into the plastically-crystalline state with β-P₄S₃?structure.

The substituted species P_4-nAs_nS_mSe_3-m (n = 0–4, m = 0–3) are formed in molten mixtures of A₄B₃?molecules (FIGURE 1). They were identified by HPLC and mass-spectrometric measurements.

After long equilibration times P₄Se₃, As₄S₃ and As₄Se₃ decompose peritectoidally into the resp. A₄B₄?species and an amorphous product.     

(Terpyridine)manganese(II) Coordination Polymers with Thio‐ and Selenidoarsenate(III) Ligands: Coligand Influence on the Chalcogenidoarsenate(III) Species and Coordination Mode

Hydrothermal reaction of [MnCl₂(terpy)] with elemental As and Se at 150 °C in 1:2:4 and 1:4:8 molar ratios in the presence of Cs₂CO₃ affords the complexes [{Mn(terpy)}₂ (As₂Se₅)]₂ ( 1 ) and [{Mn(terpy)}₂ (As₄Se₈)] ( 2 ), respectively. 1 contains dipyramidal [As₂Se₅]^4? ligands that bridge three Mn^II atoms in a tetradentate μ₃‐1κ²Se¹,Se²:2κSe⁴:3κSe⁵ manner. The tetranuclear complex is centrosymmetric and exhibits a central 8‐membered (MnSeAsSe)₂ ring. Cyclic [As₄Se₈]^4? ligands are present in the centrosymmetric dinuclear complex 2 and chelate the Mn(II) atoms through adjacent terminal Se atoms. Both 1 and 2 are linked into infinite chains through weak Mn···Se interactions. [{Mn(terpy)}₂(As₄S₈)] ( 3 ) and ( 4 ) can be obtained by hydrothermal reaction of [MnCl₂(terpy)] with As₂S₃ at respectively 150 °C and 190 °C. Whereas 3 exhibits an identical connectivity pattern to that of 2 , the coordination polymer 4 contains vierer chains that coordinate {(terpy)Mn}²⁺ fragments in a bidentate manner through terminal S atoms. The complex ( 5 ) contains double chains and results from the analogous hydrothermal reaction of [MnCl₂(tren)] with As₂S₃ at 150 °C.     

Mischkristalle aus A4B3-Molekülen (A = P,As; B = S,Se)

Mixed Crystals from A₄B₃ Molecules (A = P, As; B = S, Se) The system P₄S₃? P₄Se₃? As₄S₃? As₄Se₃ was investigated by thermal and x-ray methods. Five regions of solid solubility with different crystal structures were found at room temperature. The range of existence can be influenced by the temperature of annealing. All these phases transform into a plastic-crystalline modification with complete solid solubility at higher temperature. A decomposition reaction of the A₄B₃ molecules was observed in the P₄Se₃/As₄Se₃/As₄S₃ part of the system. The molecules decompose into A₄B₄ molecules and an amorphous phase. The existence of all molecules of the type P_nAs_4–nS_mSe_3–m (n = 0–4, m = 0–3) and also As₄S_mSe_4–m (m = 1–3) was verified by mass spectrometric measurements. The thermochemical data of the mixed crystals are determined by the type of the constituent A₄B₃ molecules. The temperature and the entropy of the α–β transition are lower for mixed crystals, formed by substituted molecules, than for those of the same structure, consisting of pure A₄B₃ molecules.     

Neue Synthesewege für Thiohalogeno- und Cyclothioarsenate(III). Kristallstrukturen von PPh4[As2SBr6] · CH3CN und PPh4[SAsS5]

Novel Routes to the Synthesis of Thiohalogeno- and Cyclothioarsenates(III). Crystal Structures of PPh₄[As₂SBr₆] · CH₃CN and PPh₄[SAsS₅] By reactions of (PPh₄)₂[As₂Cl₈] and (PPh₄)₂[As₂Br₈] with Na₂S₄ in acetonitrile (PPh₄)₂[As₂SCl₆] · CH₃CN and (PPh₄)₂[As₂SBr₆] · CH₃CN were obtained, respectively. Using K₂S₅, PPh₄[As₂SCl₅] and PPh₄[SAsS₅] were the products. The latter can also be obtained from PPh₄[As₂SCl₅] and Na₂S₄, while PPh₄[As₃S₃Br₄] is formed from PPh₄[As₂SBr₅] with K₂S₅. Two X-ray crystal structure determinations were performed. PPh₄[As₂SBr₆] · CH₃CN: triclinic, P1 , Z = 2, a = 1200.4(7), b = 1507.3(6), c = 1594.4(8) pm, α = 81.59(2), β = 78.22(3), γ = 80.58(2)°, R = 0.096 for 2298 observed reflexions. The structure contains [As₂SBr₆]^2? -ions in which the two Sb atoms are joined via one S and two Br atoms. PPh₄[SAsS₅]: triclinic, P1 , Z = 2, a = 1133.9(4), b = 1142.5(4), c = 1186.9(5) pm, α = 102.77(4), β = 107.74(3), γ = 106.65(3)°, R = 0.043 für 2677 reflexions. In the [SAsS₅]^? -ion an AsS₅ ring in the chair conformation is present.     

Reactivity in the System Copper/Arsenic/Sulfur II. The Formation of CuAsS, (Lautite)

The reaction pathways during the synthesis of CuAsS have been studied with the DTA in the range 25 — 810 °C with a heating rate of 10 K/min. Educts, intermediates, and products were characterized by X‐ray diffraction at room and elevated temperatures. Educts were the corresponding elements and the binary compounds As₄S₄, As₂S₃, Cu_3—xAs, Cu_5—δAs₂, Cu₂S, and CuS. The 13 examined educt mixtures can be divided into four groups specified by their thermal effects observed during the reaction. Mixtures of group I contain copper arsenides and arsenic sulfides, those of group II and III arsenic and copper sulfides, and arsenic sulfides and copper, respectively. Group IV includes mixtures showing individual reactions. In all cases the reaction to CuAsS proceeds stepwise. The reaction is not completed at 574 °C, the decomposition temperature of CuAsS, because the product is still associated with Cu_12+xAs_4+yS₁₃ , As, and to a lesser amount with Cu_1.81S. Nevertheless, a consecutive run in which the samples were heated above the liquidus temperature shows no exothermic reaction effect. When the mixtures were cooled at 10 K/min after the runs, no CuAsS was found in the X‐ray experiments. Only Cu_12+xAs_4+yS₁₃ and As were then observed.     

Dinuclear Manganese(II) Complexes with Bridging Selenidodiarsenate Anions [As2Se4]4−, [As2Se5]4− and [As2Se6]2−

Solvothermal reaction of [MnCl₂(amine)] (amine = terpy and tren) with elemental As and Se at a 1:1:2 molar ratio in H₂O/tren (10:1) affords the dimanganese(II) complexes [{Mn(terpy)}₂(μ‐As₂Se₄)] ( 1 ) and [{Mn(tren)}₂(μ‐As₂Se₅)] ( 2 ) respectively. The tetradentate [As₂Se₄]^4? bridging ligands in 1 contain a central As–As bond and exhibit approximately C_2h symmetry. Pairs of gauche sited Se atoms participate in five‐membered As₂Se₂Mn chelate rings. In contrast, two AsSe₃ pyramids share a common corner in the [As₂Se₅]^4? ligands of 2 and each coordinates an [Mn(tren)]²⁺ fragment through a single terminal Se atom. Such dinuclear complexes are linked into tetranuclear moieties through weak Se···Mn interactions of length 3.026(3) Å involving one of these terminal Se atoms. At a 1:3:6 molar ratio, solvothermal reaction of [MnCl₂(tren)] with As and Se leads to formation of a second dinuclear complex [{Mn(tren)}₂(μ‐As₂Se₆)₂] ( 3 ), which contains two bridging bidentate [As₂Se₆]^2? ligands. These are cyclic with an As₂Se₄ ring and can be regarded as being derived from [As₂Se₅]^4? anions by formation of two Se‐Se bonds to an additional Se atom.