Über Chalkogenolate. 198. Untersuchungen über Polythiocuprate (I) [Cu(Sx)]− 2. Hydrazinium- und Ethylendiammoniumpolythiocuprate(I)

On Chalcogenolates. 198. Studies on Polythiocuprates(I) [Cu(S_x)]^?. 2. Hydrazinium and Ethylenediammonium Polythiocuprates(I) The red polythiocuprates(I) 1–5 (formulae see ?Inhaltsübersicht”?) have been prepared by reaction of hydrazinium or ethylenediammonium polysulfides with copper(II) salts, dissolved in water, under variable conditions. Their properties are described. In aqueous alkaline media 1–5 decompose into CuS and S; in the presence of carbon disulfide CuS, S_x^2?, and CS₃^2? besides CS₄^2? and S₂CO^2? are formed. The existence of the discreet ion [Cu₂CS₇]^2?, described in literature, was not confirmed. The polythiocuprates(I) 1–5 , dissolved im dimethylformamide, decompose via the radical anion S₃^?. The decomposition of S₃^? has been studied kinetically by means of compound 5 . The half-life of decay of S₃^? is τ_1/2 = 71.5 h at 20°C. The pentathiocuprate(I) 3 reacts with n-butyl chloride to produce the substituted sulfanes (C₄H₉)₂S_x′ where x = 1, 2 and 3.     

Über Chalkogenolate. 178. Untersuchungen über Kupfer(I)-ethylxanthat

On Chalcogenolates. 178. Studies on Copper(I) Ethyl Xanthate Yellow Cu[S₂C? OC₂H₅] has been prepared by two different methods. In contrast to earlier observations it is not soluble in ethanolic solutions containing [S₂C? OC₂H₅]^? ions in excess. Cu[S₂C? OC₂H₅] reacts with CS₃^2? ions to form [Cu(CS₃)]^?. The compounds [(C₆H₅)₄E][Cu(CS₃)] with E = P, As have been isolated.     

Über Chalkogenolate. 179. Kupfer(I)-thioxanthate und Thioxanthatocuprate(I)

On Chalcogenolates. 179. Copper(I) Thioxanthates and Thioxanthatocuprates(I) Copper(I) thioxanthates Cu[S₂C? SR], where R = C₂H₅, ⁿC₄H₉, and CH₂? C₆H₅, have been prepared by two procedures and studied by means of diverse methods. They are soluble in ethanolic and acetonic solutions containing the corresponding [S₂C? SR]^? ions in excess to yield thioxanthatocuprates(I) [Cu_n(S₂C? SR)_n+1]^?. The compounds [(C₆H₅)₄P][Cu_n(S₂C? SC₂H₅)_n+1] with n = 1, 4, 6 have been isolated. The existence of [(C₆H₅)₄P][Cu₄(S₂C? SC₄H₉)₅] and [(C₆H₅)₄P][Cu₆(S₂C? SCH₂? C₆H₅)₇] has been ascertained.     

Einfache Trithio- und Perthiocarbonatokomplexe mit interessanter Koordinationschemie: [E(CS3)2]2− (E = Sn,Zn, Cd), [E(CS3)3]3− (E = As,Sb, Bi,Co), {Cu(CS3)−}∞ und [Zn(CS4)2]2−

Simple Trithio- and Perthiocarbonato Complexes with Interesting Bond Properties: [E(CS₃)₂]^2? (E = Sn, Zn, Cd), [E(CS₃)₃]^3? (E = As, Sb, Bi, Co), {Cu(CS₃)^?}_∞ and [Zn(CS₄)₂]^2? By reactions of potassium trithiocarbonate ( 1 ) with solutions of zinc(II)- acetylacetonate, cadmium(II)-chloride, tin(II)-chloride, arsenic(III)-sulfide (suspension), antimony(III)-chloride, bismuth(III)-chloride and copper(II)-chloride in dimethyl sulfoxide, as well as of trisodium hexanitrito cobaltate(III) in water, and the precipitation of the complexes with an aqueous solution of tetraphenylphosphonium chloride the compounds (PPh₄)₂[Zn(CS₃)₂] ( 2 ), (PPh₄)₂[Cd(CS₃)₂] ( 3 ), (PPh₄)₂[Sn(CS₃)₂] ( 4 ), (PPh₄)₃[As(CS₃)₃] ( 5 ), (PPh₄)₃[Sb(CS₃)₃] ( 6 ), (PPh₄)₃[Bi(CS₃)₃] ( 7 ), (PPh₄)₃[Co(CS₃)₃] ( 8 ) and (PPh₄)Cu(CS₃) ( 9 ) have been isolated. (PPh₄)₂[Zn(CS₄)₂] · CH₃NO₂ ( 10 ) has been prepared by heating a solution of 2 in nitromethane to 60--70°C in presence of air. The reaction of 1 in dimethyl sulfoxide with an aqueous tetraphenylphosphonium chloride solution in presence of oxygen leads to (PPh₄)₂[C₂S₆] ( 11 ). The compounds have been characterized by spectroscopical studies (IR, Raman, UV/Vis, ¹¹³Cd/⁵⁹Co-NMR), magnetic susceptibility measurements, powder diffractometry, elemental analyses and single crystal X-ray structure analysis ( 4 – 7 , 10 and 11 ). The difficult growing of single crystals has been reported in detail. For crystal data see Inhaltsübersicht.     

Untersuchungen an Polyhalogeniden III. Tetrammin-kupfer(II)-tetraiodid, [Cu(NH3)4I2 · I2], und Tetrammin-kupfer(II)-hexaiodid, [Cu(NH3)4I3]I3

Studies on Polyhalides. III. Crystal Structures of [Cu(NH₃)₄I₂ · I₂] and [Cu(NH₃)₄I₃]I₃ Tetramminecopper(II)tetraiodide [Cu(NH₃)₄I₂ · I₂] (I) crystallizes monoclinically in the space group C2/m with a = 1 185.9 pm, b = 892.8 pm, c = 656.8 pm, β = 111.10° and Z = 2 formula units. Tetramminecopper(II)hexaiodide [Cu(NH₃)₄I₃]I₃ (II) crystallizes orthorhombically in the space group Pnnm with a = 874.9 pm, b = 1 089.8 pm, c = 885.3 pm, and Z = 2 formula units. A special feature of these structures are coordinated polyiodide ions I₄^2? (I) or I₃^? (II). In both compounds four coplanar nitrogen atoms and two axial iodine atoms form a quasi-octahedral coordination around copper with the usual (4+2)-tetragonal distortion. The copper ions are connected by linear, centrosymmetric polyiodide ions I₄^2? (I) or I₃^? (II). Therefore infinite planar zigzag chains of units [Cu(NH₃)₄I₄] (I) or [Cu(NH₃)₄I₃]⁺(II) are resulting. The counterion I₃^? (II) is intercalated between these chains.     

Spinelle mit substituierten Nichtmetallteilgittern. VI. Röntgenographische und elektronische Eigenschaften,Mößbauer- und IR-Spektren des Spinellsystems CuCrSn(S1−xSex)4

Spinels with Substituted Nonmetal Sublattices. VI. X-Ray Investigation, Electronic Properties, Mössbauer and I.R. Spectra of the Spinel System CuCrSn(S_1?xSe_x)₄ Polycrystalline samples of the spinel system CuCrSn(S_1?xSe_x)₄ have been prepared in the range 0 ≤ x ≤ 1. The lattice constants linearly increase with x while chalcogen parameters remain constant. The calculated distances copper-chalcogen are in agreement with Cu(I). From the Mössbauer spectra we conclude that the bonding is mostly covalent and that Sn is in the oxidation state +4. The substances are p type semiconductors. Resistivities, Seebeck coefficients, and activation energies decrease with increasing x. The electrical properties are compared to those of the system ZnCr₂(S_1?xSe_x)₄. I.R. spectra have been measured from 50 cm^?1 to 600 cm^?1.     

Darstellung und Elektronenspektren neuer Trithiocarbonato-Komplexe; Struktur,Eigenschaften und Photoelektronenspektren von Ni(NH3)3CS3 und Zn(NH3)2CS3

Preparation and Electronic Spectra of new Trithiocarbonato Complexes; Structure, Properties, and Photoelectronic Spectra of Ni(NH₃)₃CS₃ and Zn(NH₃)₂CS₃ The complex anions [Zn(CS₃)₂]^2?, [Cd(CS₃)₂]^2?, [Co(CS₃)₃]^3?, [Cr(CS₃)₃]^3?, [As(CS₃)₃]^3?, [Sb(CS₃)₃]^3?, [Bi(CS₃)₃]^3?, [Sn(CS₃)₂]^2?, and [Cu(CS₃)] could be isolated as tetraphenylphosphonium and tetraphenylarsonium salts. From the electronic spectra of the transition metal complexes it follows that the CS ion exhibits, in comparison with other sulfur containing ligands, relatively large Δ-values and only a small nephelauxetic effect (e.g. in [Cr(CS₃)₃]^3?: Δ = 16.0 kK; β₃₅ = 0.57). The trithiocarbonate ion in all the above complexes acts as a bidentate ligand and forms fourmembered ring systems CS₂M. Further it was proved by means of infrared, electronic and photoelectronic spectra that the structure of “Ni(NH₃)₃CS₃” is [Ni(NH₃)₆][Ni(CS₃)₂] whereas Zn(NH₃)₂CS₃ has not such an ionic structure.     

Reactivity of Liquid Ammonia Solutions of the Zintl Phase K12Sn17 towards Mesitylcopper(I) and Phosphinegold(I) Chloride

To gain more insight into the reactivity of intermetalloid clusters, the reactivity of the Zintl phase K₁₂Sn₁₇, which contains [Sn₄]^4? and [Sn₉]^4? cluster anions, was investigated. The reaction of K₁₂Sn₁₇ with gold(I) phosphine chloride yielded K₇[(η²‐Sn₄)Au(η²‐Sn₄)](NH₃)₁₆ ( 1 ) and K₁₇[(η²‐Sn₄)Au(η²‐Sn₄)]₂(NH₂)₃(NH₃)₅₂ ( 2 ), which both contain the anion [(Sn₄)Au(Sn₄)]^7? ( 1 a ) that consists of two [Sn₄]^4? tetrahedra linked through a central gold atom. Anion 1 a represents the first binary Au?Sn polyanion. From this reaction, the solvate structure [K([2.2.2]crypt)]₃K[Sn₉](NH₃)₁₈ ( 3 ; [2.2.2]crypt=4,7,13,16,21,24‐hexaoxa‐1,10‐diazabicyclo[8.8.8]hexacosane) was also obtained. In the analogous reaction of mesitylcopper with K₁₂Sn₁₇ in the presence of [18]crown‐6 in liquid ammonia, crystals of the composition [K([18]crown‐6)]₂[K([18]crown‐6)(MesH)(NH₃)][Cu@Sn₉](thf) ( 4 ) were isolated ([18]crown‐6=1,4,7,10,13,16‐hexaoxacyclooctadiene, MesH=mesitylene, thf=tetrahydrofuran) and featured a [Cu@Sn₉]^3? cluster. A similar reaction with [2.2.2]crypt as a sequestering agent led to the formation of crystals of [K[2.2.2]crypt][MesCuMes] ( 5 ). The cocrystallization of mesitylene in 4 and the presence of [MesCuMes]^? ( 5 a ) in 5 provides strong evidence that the migration of a bare Cu atom into an Sn₉ anion takes place through the release of a Mes^? anion from mesitylcopper, which either migrates to another mesitylcopper to form 5 a or is subsequently protonated to give MesH.     

Darstellung von trans-[Pt(N3)4X2]2− (X = Br,I, SCN,SeCN) durch oxidative Addition an [Pt(N3)4]2− in organischen Lösungsmitteln

Preparation of trans-[Pt(N₃)₄X₂]^2? (X ? Br, I, SCN, SeCN) by Oxidative Addition to [Pt(N₃)₄]^2? in Organic Solvents By oxidative addition to (TBA)₂[Pt(N₃)₄], dissolved in dichlormethane, trans-(TBA)₂[Pt(N₃)₄X₂], X ? Br, I, SCN, SeCN; TBA = Tetrabutylammonium, are formed. The vibrational spectra of these salts are assigned according to point group D_4h. From the resonance Raman spectrum of trans-(TBA)₂[Pt(N₃)₄I₂] the harmonic vibrational frequency ω₁ of v(Pt? I), A_1g, is calculated to be 138.50 cm^?1 and the inharmonicity constant x₁₁ = 0.27 cm^?1. The characteristical feature in the UV/VIS spectra is caused by intensive π(N,X) → a_1g, b_1g(Pt) CT transitions.     

Structural Characterization of Some Coinage Metal(I) Thiosulfate Complexes, $\rm M^{1}_{a}M\rm ^{2}_{b}(X_{c}) (S_{2}O_{3})_{d}(\cdot eS)$ (M1 = Group 1 Cation,X = Univalent Anion,M2 = CuI,AgI, S = Solvent)

Building on previous single crystal X‐ray structure determinations for the group 1 salts of complex thiosulfate/univalent coinage metal anions previously defined for (NH₄)₉AgCl₂(S₂O₃)₄, NaAgS₂O₃·H₂O and Na₄[Cu(NH₃)₄][Cu(S₂O₃)₂]·NH₃, a wide variety of similar salts, of the form , M¹ = group 1 metal cation, M² = univalent coinage metal cation (Cu, Ag), (X = univalent anion), most previously known, but some not, have been isolated and subjected to similar determinations. These have defined further members of the isotypic, tetragonal series, for M¹ = NH₄, M² = Cu, Ag, X = NO₃, Cl, Br, I, together with the K/Cu/NO₃ complex, all containing the complex anion [M²(SSO₃)₄]^7? with M² in an environment of symmetry, Cu, Ag‐S typically ca. 2.37, 2.58Å, with quasi‐tetrahedral S‐M‐S angular environments. Further salts of the form , n = 1‐3, have also been defined: For n = 3, M² = Cu, M¹/x = K/2.25 or 1 5/6, NH₄/6, (and also for the (NH₄)₄Na/4H₂O·MeOH adduct) the arrays take the form with distorted trigonal planar CuS₃ coordination environments, Cu‐S distances being typically 2.21Å, S‐Cu‐S ranging between 105.31(4)–129.77(4)°; the silver counterparts take the form for M¹ = K, NH₄. For n = 2, adducts have only been defined for M² = Ag, the anions of the M¹ = Na, K adducts being dimeric and polymeric respectively: Na₆[(O₃SS)₂Ag(μ‐SSO₃)₂Ag(SSO₃)]·3H₂O, K₃[Ag(μ‐SSO₃)₂]_(∞|∞)·H₂O; a polymeric copper(I) counterpart of the latter is found in Na₅Cu(NO₃)₂(S₂O₃)₂ ≡ 2NaNO₃·Na₃[Cu(μ‐SSO₃)₂]_(∞|∞). For n = 1, NaAgS₂O₃, the an‐ and mono‐ hydrates, exhibit a two‐dimensional polymeric complex anion in both forms but with different contributing motifs. (NH₄)₁₃Ag₃(S₂O₃)₈·2H₂O takes the form (NH₄)₁₃[{(O₃SS)₃Ag(μ‐SSO₃)}₂Ag], a linearly coordinated central silver atom linking a pair of peripheral [Ag(SSO₃)₄]^7? entities. In Na₆[(O₃SS)Ag(μ‐SSO₃)₂Ag(SSO₃)]·3H₂O, the binuclear anions present as Ag₂S₄ sheets, the associated oxygen atoms being disposed to one side, thus sandwiching layers of sodium ions; the remarkable complex Na₅[Ag₃(S₂O₃)₄]_(∞|∞)·H₂O is a variant, in which one sodium atom is transformed into silver, linking the binuclear species into a one‐dimensional polymer. In (NH₄)₈[Cu₂(S₂O₃)₅]·2H₂O a binuclear anion of the form [(O₃SS)₂Cu(μ‐S.SO₃)Cu(SSO₃)₂]^8? is found; the complex (NH₄)₁₁Cu(S₂O₃)₆ is 2(NH₄)₂(S₂O₃)·(NH₄)₇[Cu(SSO₃)₄]. A novel new hydrate of sodium thiosulfate is described, 4Na₄S₂O₃·5H₂O, largely describable as sheets of the salt, shrouded in water molecules to either side, together with a redetermination of the structure of 3K₂S₂O₃·H₂O.     

Über Chalkogenolate. 163. Umsetzungen von Hydrazin mit Kohlenstoffdisulfid. 2. Kristallstruktur von Dikalium-1,2-hydrazin-bis(dithioformiat)

On Chalcogenolates. 163. Reactions of Hydrazine with Carbon Disulfide. 2. Crystal Structure of Dipotassium 1,2-Hydrazine-bis (dithioformate) The title compound K₂[S₂C? NH? NH? CS₂] ( 1 ) crystallizes with Z = 4 in the orthorhombic space group Pbna with cell dimensions a = 6.635(1), b = 10.825(2), c = 12.866(2) Å. The crystal structure has been determined from single crystal X-ray data measured at ?85 °C and refined to a conventional R of 0.034 for 969 independent reflections (R_w = 0.042). The [S₂C? NH? NH? CS₂]^2? ions are linked together by hydrogen bridges N? H…?S. The K⁺ ions are surrounded by seven sulfur atoms in irregular coordination.     

Über [Ag(S9)]−, ein symmetrisches zehngliedriges Ringsystem Darstellung,Struktur und spektroskopische Charakterisierung der schwefelreichen Verbindung [(PPh3)2N][Ag(S9)] · S8

About [Ag(S₉)]^?, a Symmetric Ten-Membered Ring System; Preparation, Structure, and Spectroscopic Characterization of the Sulfur Rich Compound [(PPh₃)₂N][Ag(S₉)] · S₈ Orange [(PPh₃)₂N][Ag(S₉)] · S₈ ( 1 ) could be obtained by reaction of a definite S_x^2?-solution with AgNO₃ and characterized by vibrational spectra (IR/Raman) and X-ray structure analysis. The anion [Ag(S₉)]^? shows a symmetric conformation of a ten-membered ring system. 1 crystallizes in the triclinic space group P1 (a = 1383.8(4), b = 1429.5(4), c = 1540.5(5) pm, α 62.38(2), β 68.05(2), γ 65.86(2)°, V = 2399.1 · 10⁶ pm³, Z = 2; R = 0.077 for 5433 independent reflections (F₀ > 3.92 σ(F₀))).     

Polysulfonylamine. XL Darstellung von Silber(I)-disulfonylamid-Acetonitril-Komplexen. Röntgenstrukturanalytische und thermochemische Charakterisierung von Tetraacetonitrilsilber(I)-bis(dimesylamido)argentat(I) und von (1,1,3,3-Tetraoxo-1,3,2-benzodithiazolido)acetonitrilsilber(I)

Polysulfonyl Amines. XL. Preparation of Silver(I) Disulfonylamide Acetonitrile Complexes. Characterization of Tetraacetonitrilesilver(I) bis(dimesylamido)argentate(I) and (1,1,3,3-Tetraoxo-1,3,2-benzodithiazolido)acetonitrilesilver(I) by X-Ray Diffractometry and Thermal Analysis The following silver(I) disulfonylamides were prepared for the first time or by improved procedures: AgN(SO₂CH₃)₂ ( 2a ); AgN(SO₂C₆H₄-4-X)₂ with X = F ( 2b ), Cl ( 2c ), Br ( 2d ), CH₃ ( 2e ); silver(I) 1,2-benzenedisulfonimide AgN(SO₂)₂C₆H₄ ( 2f ). With acetonitrile, the salts 2a to 2e form (1/2) complexes AgN(SO₂R)· 2 CH₃CN ( 4a to 4e ), whereas 2f gives the (1/1) complex AgN(SO₂)₂C₆H · CH₃CN ( 4f ). The crystallographic data (at - 95°C) for the title compounds 4a and 4f are: 4a , space group C2/c, a = 1 967.6(4), b = 562.2(1), c = 2 353.0(5) pm, β = 102.21(2)°, V = 2.5440 nm³, Z = 4, D_x = 1.891 Mg m^?3; 4f , space group P2₁/m, a = 741.5(3), b = 980.4(4), c = 756.6(3) pm, β = 99.28(2)°, V = 0.5428 nm³, Z = 2, D_x = 2.246 Mg m^?3. 4a forms an ionic crystal [Ag(NCCH₃)₄]^⊕[Ag{N(SO₂CH₃)₂}₂]^? with a tetrahedrally coordinated silver atom (lying on a twofold axis) in the cation (225.3/225.7 pm for the two independent Ag? N distances, N? Ag? N 106.2—114.5°) and a linear-dicoordinated silver atom in the centrosymmetric anion (Ag? N 213.9 pm, two intraionic secondary Ag…O contacts 303.4 pm). 4f consists of uncharged molecules [C₆H₄(SO₂)₂N¹AgN²CCH₃] with crystallographic mirror symmetry (Ag? N¹ 218.8, Ag? N² 216.1 pm, N¹? Ag? N² 174.3°), associated into strands by intermolecular secondary silver-oxygen contacts (Ag…O 273.8 pm, O…Ag…O 175.6, N? Ag…O 91.9/88.2°). The thermochemical behaviour of 4f was investigated using thermogravimetry, differential scanning calorimetry (DSC), time- and temperature-resolved X-ray diffractometry (TXRD), and solution calorimetry. The desolvation process occurs in the temperature range from 60 to 200°C and appears to be complex, although no crystalline intermediate could be detected. The desolvation enthalpy at 298 K was found to be + 26.8(4) kJ mol^?1. 4a is desolvated in two steps at - 15 to 60°C and 60 to 95°C (DSC), suggesting the formation of AgN(SO₂CH₃) · CH₃CN as an intermediate.     

Über Chalkogenolate. 164. Umsetzungen von Hydrazin mit Kohlenstoffdisulfid. 3. Synthese und Charakterisierung von Trinatrium-1,2-hydrazin-bis(dithiocarboxylat)

On Chalcogenolates. 164. Reactions of Hydrazine with Carbon Disulfide. 3. Synthesis and Characterization of Trisodium 1,2-Hydrazine-bis(dithiocarboxylate) The mixed dithiocarbamate-dithiocarbimate Na₃[S₂C? NH? N°CS₂] · 7 H₂O has been prepared by reaction of H₂N? NH₂ · H₂O with CS₂ and NaOH in aqueous solution. It has been characterized by means of diverse methods.     

Über Chalkogenolate. 159. Umsetzung von 1,2-Ethandithiolaten mit Kohlenstoffdisulfid 1. Darstellung und Eigenschaften von 1,2-Ethan-bis(trithiocarbonaten)

On Chalcogenolates. 159. Reaction of 1,2-Ethanedithiolates with Carbon Disulfide. 1. Synthesis and Characterization of 1,2-Ethane-bis(trithiocarbonates) The reaction of 1,2-ethanedithiolates with carbon disulfide forms the corresponding 1,2-ethane-bis(trithiocarbonates). The compounds M₂[S₂C? SCH₂CH₂S? CS₂] with M = Li, Na, K, Rb, Cs, NH₄, Tl have been characterized with chemical methods as well as by means of electron absorption, infrared, nuclear magnetic resonance (¹H and ¹³C), and mass spectra.     

Einstieg in die Chemie einfacher Rhenium-Schwefel-Komplexe und -Cluster. Darstellung und Kristall-Struktur von R[ReS4], R′[ReS9], (NH4)4[Re4S22]·2H2O,R′2[Cl2Fe(MoS4)FeCl2]x [Cl2Fe(ReS4)FeCl2]1-x′ R′2 [(ReS4)Cu3l4] und RR′2[(ReS4)Cu5Br7] (R  NEt4; R′  PPh4; x = 0,3, 0,5)

Entry to the Chemistry of Simple Rhenium Sulfur Complexes and Clusters. Preparation and Crystal Structures of R′[ReS₄], R′[ReS₉], (NH₄)₄[Re₄S₂₂]·2H₂O, R′₂[Cl₂Fe(MoS₄)FeCl₂]_1-x, R′₂[(ReS₄)Cu₃I₄] and RR′₂[(ReS₄)Cu₅Br₇] (R ? NEt₄; R′ ? PPh₄, x = 0.3, 0.5) The compounds R[ReS₄] ( 1 ), R′[ReS₉] ( 2 ), (NH₄)₄[Re₄S₂₂]·2 H₂O ( 3 ), R′₂[Cl₂Fe(MoS₄) FeCl₂]_x[Cl₂Fe(ReS₄)FeCl₂] _1-x (x = 0.3 ( 4 ), 0.5), R′₂[(ReS₄)Cu₃I₄] ( 5 ) and R′₂[(ReS₄)Cu₅Br₇] ( 6 ) (R ? NEt₄; R′ ? PPh₄) have been prepared by reaction of perrhenates or rhenium(VII)oxide with S_x^2? solutions (under different conditions) or by reactions of metal-halides with [ReS₄]^?-ions. All compounds have been characterized by complete X- ray structure analysis. For further details see Inhaltsübersicht.     

Spinelle mit substituierten Nichtmetallteilgittern. VIII. Röntgenographische und elektrische Eigenschaften,Mößbauer- und IR-Spektren des Systems FeCr2(S1−xSex)4

Spinels with Substituted Nonmetal Sublattices. VIII. X-Ray Investigation, Electric Properties, Mössbauer and I.R. Spectra of the System FeCr₂(S_1?xSe_x)₄ In the system FeCr₂(S_1?xSe_x)₄ the spinel structure exists in the range 0 ≤ x ≤ 0.3₃, the monoclinic Cr₃S₄-structure in the range 0.6 ≤ x ≤ 1. Lattice parameters have been determined and I.R. spectra have been measured between 200 cm^?1 and 600 cm^?1. Room temperature Mössbauer spectra consist of several overlapping doublets of almost identical isomer shifts but different quadrupole splittings. The Fe doublets are attributed to the coordination polyhedrons S₄, S₃Se and S₂Se₂. The spinels are p type semiconductors.     

UF6 and UF4 in Liquid Ammonia: [UF7(NH3)]3− and [UF4(NH3)4]

From the reaction of uranium hexafluoride UF₆ with dry liquid ammonia, the [UF₇(NH₃)]^3? anion and the [UF₄(NH₃)₄] molecule were isolated and identified for the first time. They are found in signal‐green crystals of trisammonium monoammine heptafluorouranate(IV) ammonia (1:1; [NH₄]₃[UF₇(NH₃)] ? NH₃) and emerald‐green crystals of tetraammine tetrafluorouranium(IV) ammonia (1:1; [UF₄(NH₃)₄] ? NH₃). [NH₄]₃[UF₇(NH₃)] ? NH₃ features discrete [UF₇(NH₃)]^3? anions with a coordination geometry similar to a bicapped trigonal prism, hitherto unknown for U^IV compounds. The emerald‐green [UF₄(NH₃)₄] ? NH₃ contains discrete tetraammine tetrafluorouranium(IV) [UF₄(NH₃)₄] molecules. [UF₄(NH₃)₄] ? NH₃ is not stable at room temperature and forms pastel‐green [UF₄(NH₃)₄] as a powder that is surprisingly stable up to 147 °C. The compounds are the first structurally characterized ammonia complexes of uranium fluorides.     

Heteronukleare Komplexverbindungen mit Metall—Metall-Bindungen. VIII. Neue heterodinukleare Komplexe mit Bindungen zwischen Kupfer(I) und Mangan(–I), Eisen(–I) oder Cobalt(–I)

Heteronuclear Coordination Compounds with Metal—Metal Bonds. VIII. New Heterodinuclear Complexes with Bonds between Copper(I) and Manganese(?I), Iron(?I), or Cobalt(?I) [(en)Cu? Mn(CO)₅] ( 1a ), [(dien)Cu? Mn(CO)₅] ( 1b ), [(en)Cu? Fe(CO)₃(NO)] ( 2a ), [(dien)Cu? Fe(CO)₃(NO)] ( 2b ), [(en)Cu? Co(CO)₄] ( 3a ), and [(dien)Cu? Co(CO)₄] ( 3b ) are new heterobinuclear metal—metal bonded complexes. The geometry of the [Mn(CO)₅]^?, [Fe(CO)₃(NO)]^?, and [Co(CO)₄]^? ions is distorted only to a less extend in accord with a heteropolar bond to copper.     

The thermal decomposition of (NH4)4V2O11 in a nitrogen atmosphere and the kinetics of the first decomposition step

Although the reaction products are unstable at the reaction temperatures, at a heating rate of 2 deg·min^?1 ammonium peroxo vanadate, (NH₄)₄V₂O₁₁, decomposes to (NH₄)[VO (O₂)₂ (NH₃)] (above 93°C); this in turn decomposes to (NH₄) [VO₃ (NH₃)] (above 106°C) and then to ammonium metavanadate (above 145°C). On further heating vanadium pentoxide is formed above 320°C. The first decomposition reaction occurs in a single step and the Avrami-Erofeev equation withn=2 fits the decomposition data best. An activation energy of 148.8 kJ·mol^?1 and a ln(A) value of 42.2 are calculated for this reaction by the isothermal analysis method. An average value of 144 kJ·mol^?1 is calculated for the first decomposition reaction using the dynamic heating data and the transformation-degree dependence of temperature at different heating rates.