PPh4[As3S3Cl4] und PPh4[As3S3Br4]

PPh₄[As₃S₃Cl₄] and PPh₄[As₃S₃Br₄] When As₂S₃ reacts with PPh₄X and HX in 1,2-C₂H₄X₂ (X = Cl, Br), the title compounds are obtained as minor products; the main products are PPh₄[As₂SX₅]. Their crystal structures were determined by X-ray diffraction. PPh₄[As₃S₃Cl₄]: a = 1187.7, b = 1090.9, c = 1191.8 pm, α = 82.91, β = 88,93, γ = 88.52°; twins with twin plane (100); R = 0.109 for 1618 observed reflexions of one twin crystal. PPh₄[As₃S₃Br₄]: a = 1119.7, b = 1177.5, c = 1204.1 pm, α = 81.59, β = 85.88, γ = 88.25°; R = 0.061 for 2331 observed reflexions. Both compounds crystallize in the space group P1 , Z = 2, and can be considered to be isotypic. Nevertheless, PPh₄[As₃S₃Br₄] does not form twins as PPh₄[As₃S₃Cl₄]. The crystals consist of PPh₄⁺ and [As₃S₃X₄]^? ions. In the anions, the three As atoms of an As₃S₃ ring in the chair conformation are commonly joined to an X atom and each As atom is bonded to one further terminal X atom. Cations and anions are packed in alternating layers.     

Die Bromokomplexe von Molybdän(IV) [MoBr6]2⊖ und [Mo2Br10]2⊖. Die Kristallstruktur von (PPh3Me)2[MoBr6] · 2 CH2Br2

Bromo Complexes of Molybdenum(IV) [MoBr₆]^2? and [Mo₂Br₁₀]^2?. Crystal Structure of (PPh₃Me)₂[MoBr₆] · 2 CH₂Br₂ The bromomolybdates(IV) (PPh₃Me)₂[MoBr₆] · 2 CH₂Br₂ and (PPh₄)₂[Mo₂Br₁₀] are obtained by reactions of molybdenum tetrabromide with PPh₃MeBr and PPh₄Br, respectively. They form black-brown, hydrolysis sensitive crystal powders. The crystal structure of (PPh₃Me)₂[MoBr₆] · 2 CH₂Br₂ was determined by X-ray diffraction (2376 independent observed reflexions, R = 0.082). Crystal data: a = 1024, b = 1131, c = 1179 pm, α = 108.2°, β = 106.8°, γ = 99.0°, space group P1 , Z = 1. The compound consists of PPh₃Me⁺ ions, CH₂Br₂ molecules and nearly octahedral [MoBr₆]^2? ions with MoBr bond lengths between 252.7 and 254.0 pm.     

Pentabromothio-diarsenat und -diantimonat: Darstellung,Schwingungsspektren und Kristallstrukturen von PPh4[As2SBr5] und PPh4[Sb2SBr5]

Pentabromothio-diarsenate and -diantimonate: Preparation, Vibrational Spectra, and Crystal Structures of PPh₄[As₂SBr₅] and PPh₄[Sb₂SBr₅] The title compounds were obtained in CH₂Br₂ from PPh₄Br, HBr and As₂S₃ or Sb₂S₃, respectively. Their i.r. and Raman spectra are reported. Their crystal structures were determined by X-ray diffraction. Crystal data: PPh₄[As₂SBr₅], monoclinic, space group P2₁/n, Z = 4, a = 1192.3, b = 1528.1, c = 1618.0 pm, β = 95.53°, isotypic with PPh₄[As₂SCl₅] (structure determination with 1539 observed reflexions, R = 0.052); PPh₄[Sb₂SBr₅], triclinic, space group P1 , Z = 2, a = 1044,8, b = 1207.1, c = 1307.8 pm, α = 104.77, β = 108.63, γ = 98.34° (2398 observed reflexions, R = 0.032). Both ions, [As₂SBr₅]^? and [Sb₂SBr₅]^?, have the same general structure: including the lone electron pairs, the As and Sb atoms have distorted trigonal-bipyrimidal coordination, two bipyramids sharing a common edge with sulfur and bromine as bridging atoms. The [As₂SBr₅]^? ions are associated to chains via As…Br contacts, the [Sb₂SBr₅]^? ions form pseudodimeric units by Sb…S and Sb…Br contacts. Whereas the crystal packing of the As compound is similar to that of other PPh₄⁺ compounds having a cation to anion ratio of 1:1, the Sb compound shows the packing principle known for 2:1 compounds.     

EPR- und Ligandenfeld-Spektren von Chlorovanadaten(IV). Die Kristallstruktur von PPh4[VxTi2–xCl9] (x = 0,15)

E.P.R. and Ligand Field Spectra of Chlorovanadates(IV). The Crystal Structure of PPh₄[V_xTi_2–xCl₉] (x = 0.15) Black, moisture-sensitive crystals of PPh₄[V_xTi_2–xCl₉] (x = 0.15) are formed by the reaction of titanium tetrachloride and PPh₄[VCl₅] in dichloromethane. Its EPR and ligand field spectra as well as those of PPh₄[VCl₅] and (PPh₄)₂[V₂Cl₉][VCl₅] · CH₂Cl₂ were recorded. In the mixed crystals of PPh₄[V_0.15Ti_1.85Cl₉], the existence of [VTiCl₉]^? ions consisting of trigonally distorted, face sharing octahedra can be proven by the spectra. The spectra of the compounds with [VCl₅]^? ions can only be explained when a significant Jahn-Teller distortion of the trigonal bipyramids is assumed; this distortion was not detected in the crystal structure determination of (PPh₄)₂[V₂Cl₉][VCl₅] · CH₂Cl₂. The crystal structure of PPh₄[V_0.15Ti_1.85Cl₉] was determined by X-ray diffraction (2588 independent observed reflexions, R = 0.044). Crystal data: triclinic, space group P1 , a = 1090.4, b = 1217.4, c = 1287.7 pm, α = 73.19°, β = 69.87°, γ = 82.15°, Z = 2. The compound consists of PPh₄^⊕ and [V_0.15Ti_1.85Cl₉]^? ions. In the anions, Ti and V atoms are distributed statistically in the two face sharing octahedra.     

Synthese und Kristallstrukturen von (PPh4)2[As2Se4Cl12] und (PPh4)2[As2Se4Br12]

Synthesis and Crystal Structures of (PPh₄)₂[As₂Se₄Cl₁₂] and (PPh₄)₂[As₂Se₄Br₁₂] The reaction of PPh₄Cl and As₂Se₃ with SOCl₂ or with chlorine in dichloromethane affords (PPh₄)₂[As₂Se₄Cl₁₂] with good yields. From PPh₄Br, As₂Se₃ and bromine the corresponding bromo compound was obtained. According to the X-ray crystal structure determinations both compounds are isotypic, crystallizing in the space group of P1 . In the anions two Se₂X₂ molecules are linked with two X^? ions forming an Se₄X₂ ring in chair conformation. Each X^?-ion is associated with an additional AsX₃ molecule (X = Cl, Br).     

Ein- und zweikernige Dinitrosylkomplexe von Molybdän und Wolfram. Die Kristallstrukturen von (PPh3Me)2[WCl4(NO)2], (PPh3Me)2[MoCl3(NO)2]2 und von (PPh3Me)2[WCl3(NO)2]2

Mono- and Binuclear Dinitrosyl Complexes of Molybdenum and Tungsten. Crystal Structures of (PPh₃Me)₂[WCl₄(NO)₂], (PPh₃Me)₂[MoCl₃(NO)₂]₂, and (PPh₃Me)₂[WCl₃(NO)₂]₂ The complexes (PPh₃Me)₂[MCl₄(NO)₂] (M = Mo, W), and (PPh₃Me)₂[MCl₃(NO)₂]₂, respectively, are prepared by reactions of the polymeric compounds MCl₂(NO)₂ with triphenylmethylphosphonium chloride in CH₂Cl₂, forming green crystals. According to the IR spectra the nitrosyl groups are in cis-position in all cases. The tungsten compounds as well as (PPh₃Me)₂[MoCl₃(NO)₂]₂ were characterized by structure determinations with X-ray methods. (PPh₃Me)₂[WCl₄(NO)₂]: space group C2/c, Z = 4. a = 1874, b = 1046, c = 2263 pm, β = 119.99°. Structure determination with 3492 independent reflexions, R = 0.057. The compound consists of PPh₃Me^⊕ ions, and anions [WCl₄(NO)₂]^2? with the nitrosyl groups in cis-position (symmetry C_2v). (PPh₃Me)₂[WCl₃(NO)₂]₂: Space group C2/c, Z = 4. Structure determination with 2947 independent reflexions, R = 0.059. (PPH₃Me)₂[MoCl₃(NO)₂]₂: Space group P1 , Z = 1. a = 989, b = 1134, c = 1186 pm; α = 63.25°, β = 80.69°, γ = 69.94°. Structure determination with 3326 independent reflexions, R = 0.046. The compounds consist of PPh₃Me^⊕ ions, and centrosymmetric anions [MCl₃(NO)₂]₂^2?, in which the metal atoms are associated via MCl₂M bridges of slightly different lengths. One of the NO groups is in an axial position, the other one in equatorial position (symmetry C_2h).     

Thiochloro-Verbindungen von fünfwertigem Niob und Wolfram: WSCl3, [WSCl4]22−, [NbSCl4]− Die Kristallstruktur von PPh4[NbSCl4]

Thio-chloro Compounds of Pentavalent Niobium and Tungsten: WSCl₃, [WSCl₄]₂^2?, [WSCl₅]^2?, [NbSCl₄]^?. Crystal Structure of PPh₄[NbSCl₄] Black WSCl₃ was obtained by reduction of (WSCl₄)₂ with C₂Cl₄. With PPh₄Cl in CH₂Cl₂ it yields (PPh₄)₂[WSCl₄]₂ which has a dimeric structure with chloro bridges according to its i. r. spectrum. Iodide reduces PPh₃Me[WSCl₅] in CH₂Cl₂ to (PPh₃Me)₂[WSCl₅], from which (PPh₃Me)₂[WSBr₅ · BBr₃] is obtained by reaction with BBr₃. From PPh₄Cl in CH₂Cl₂ and raw NbSCl₃ (obtained by solid state reaction of NbCl₅ with B₂S₃) PPh₄[NbSCl₄] is formed. The crystal structure of PPh₄-[NbSCl₄] was determined and refined with X-ray diffraction data (residual index R = 0.066 for 1017 reflexions). It crystallizes in the AsPh₄[RuNCl₄] structure type (space group P4/n) with the lattice constants a = 1303 and c = 760 pm. The quadratic-pyramidal [NbSCl₄]^? ion has a Nb?S bond length of 209 pm. The i. r. spectra of all compounds are discussed.     

Reaktionen von Uranpentabromid Die Kristallstrukturen von PPh4[UBr6], PPh4 [UBr6] · 2CCl4, (PPh4)2[UBr6] · 4CH3CN und (PPh4)2[UO2Br4] · 2CH2Cl2

Reactions of Uranium Pentabromide. Crystal Structures of PPh₄[UBr₆], PPh₄[UBr₆] · 2CCl₄, (PPh₄)₂[UBr₆] · 4CH₃CN, and (PPh₄)₂[UO₂Br₄] · 2CH₂Cl₂ PPh₄[UBr₆] and PPh₄[UBr₆] · 2CCl₄ were obtained from UBr₅ · CH₃CN and tetraphenylphosphonium bromide in dichloromethane, the latter being precipitated by CCl₄. Their crystal structures were determined by X-ray diffraction. PPh₄[UBr₆]: 2101 observed reflexions, R = 0.090, space group C2/c, Z = 4, a = 2315.5, b = 695.0, c = 1805.2 pm, β = 96.38°. PPh₄[UBr₆] · 2CCl₄: 2973 reflexions, R = 0.074, space group P2₁/c, Z = 4, a = 1111.5, b = 2114.2, c = 1718.7 pm, β = 95.42°. Hydrogen sulfide reduces uranium pentabromide to uranium tetrabromide. Upon evaporation, bromide is evolved from solutions of UBr₅ with 1 or more then 3 mol equivalents of acetonitrile in dichlormethane yielding UBr₄ · CH₃CN and UBr₄ · 3CH₃CN, respectively. These react with PPh₄Br in acetonitrile affording (PPh₄)₂[UBr₆] · 4CH₃CN, the crystal structure of which was determined: 2663 reflexions, R = 0.050, space group P2₁/c, Z = 2, a = 981.8, b = 2010.1, c = 1549.3 pm, β = 98.79°. By reduction of uranium pentabromide with tetraethylammonium hydrogen sulfide in dichloromethane (NEt₄)₂[U₂Br₁₀] was obtained; (PPh₄)₂[U₂Br₁₀] formed from UBr₄ and PPh₄Br in CH₂Cl₂. Both compounds are extremely sensitive towards moisture and oxygen. The crystal structure of the oxydation product of the latter compound, (PPh₄)₂[U0₂Br₄]· 2 CH₂Cl₂, was determined: 2163 reflexions, R = 0.083, space group C2/c, Z = 4, a = 2006.3, b = 1320.6, c = 2042,5 pm, β = 98.78°. Mean values for the UBr bond lengths in the octahedral anions are 266.2 pm for UBr₆-, 276.7 pm for UBr₆^2? and 282.5 pm for UO₂Br₄^2?     

Disulfidoverbrückte Halogenokomplexe von Molybdän(V) Kristallstrukturen von (PPh3Me)2[Cl4Mo(μ-S2)2MoCl4] · 2 CH2Cl2 und (PPh4)2[Br4Mo(μ-S2)2MoBr4] · 3 CH2Br2

Disulfido-Bridged Halo Complexes of Molybdenum (V). Crystal Sructures of (PPh₃Me)₂ [Cl₄Mo (μ-S₂)₂MoCl₄]. 2 CH₂Cl₂ and (PPh₄)₂[Br₄Mo(μ-S₂)₂MoBr₄]. 3CH₂Br₂ . Mo(S₂)Cl₃ is prepared by an improved method; the i.r. spectrum is reported. In dichloro methane solution it reacts with (PPh₃Me)Cl forming the complex (PPh₃Me)₂[Cl₄Mo(μ-S₂)₂MoCl₄] · 2 CH₂Cl₂. The bromo complex (PPh₄)₂[Br₄Mo(μ-S₂)₂MoBr₄] · 3 CH₂Br₂ is obtained by reaction of MoBr₄ with S₇NH and subsequent treatment of the reaction mixture with PPh₄Br in CH₂Br₂ solution. Both complexes are characterized by i.r. spectra and structural analyses by X-ray methods. (PPh₃Me)₂[Cl₄Mo(μ-S₂)₂MoCl₄] · 2 CH₂Cl₂ crystallizes monoclinic in the space group P2₁/c with two formula units per unit cell (5268 observed independent reflexions, R = 4.0%). The lattice dimensions are: a = 1097 pm, b = 1510 pm, c = 1591 pm, β = 104.4°. (PPh₄)₂[Br₄Mo(μ-S₂)₂MoBr₄] · 3 CH₂Br₂ crystallizes triclinic in the space group P&1macr; with two formula units per unit cell and the lattice constants a = 1328 pm, b = 1573 pm, c = 1719 pm, α = 95.8°, β = 96.3°, γ = 74.1°. Both compounds are of ionical structure with PPh₃Me^⊕ and PPh₄^⊕ cations, respectively, and anions [X₄MO(μ-S₂)₂MoX₄]^2? very similar to each other. The molybdenum atoms are bridged by two disulfido ligands and are bonded directly with a bond length of 286 pm. The terminal halogen atoms add up to coordination number nine at the molybdenum.     

Thiochlorowolframate von Wolfram(V) und -(VI). Die Kristallstrukturen von PPh4[WSCl4] und (PPh4)2[WS2Cl4] · 2 CH2Cl2

Thiochlorowolframates with Tungsten(V) and (VI). Crystal Structures of PPh₄[WSCl₄] and (PPh₄)₂[WS₂Cl₄] · 2 CH₂Cl₂ Diamagnetic (NEt₄)₂[WSCl₄]₂, having tungsten atoms linked via sulfur atoms, is obtained by the reaction of WCl₅ with NEt₄SH as well as by the reduction of WSCl₄ with NEt₄I in dichloromethane. If the reduction is performed with PPh₄I, PPh₄[WSCl₄] with monomer anions is formed. Reaction of WCl₆ with H₂S in dichloromethane yields brown, insoluble WS₂Cl₂ which has terminal W?S groups and bridging W? S? W groups according to its IR spectrum. WS₂Cl₂ and PPh₄Cl react to afford PPh₄[WS₂Cl₃] · 2 CH₂Cl₂ and (PPh₄)₂[WS₂Cl₄] · 2 CH₂Cl₂. IR spectra are reported. The crystal structures of PPh₄[WSCl₄] and (PPh₄)₂[WS₂Cl₄] · 2 CH₂Cl₂ were determined by X-ray diffraction. PPh₄[WSCl₄]: tetragonal, space group P4/n, Z = 2, a = 1292.3 pm, c = 763.2 pm; R = 0.054 for 898 observed reflexions. The [WSCl₄]^? ion has the structure of a square pyramid with a rather short W?S bond of 206 pm length. (PPh₄)₂[WS₂Cl₄] · 2 CH₂Cl₂: triclinic, space group P1 , a = 1017.7, b = 1114.5, c = 1243.4 pm, α = 70.61, β = 79.73, γ = 80.80°; R = 0.076 for 1804 reflexions. The [WS₂Cl₄]^2? has cis configuration; as it is situated on an inversion center it shows positional disorder.     

Die Kristallstrukturen von [ReCl4(PhCCPh)]2 · 2 CH2Cl2 und von PPh4[ReOCl4]

Crystal Structures of [ReCl₄(PhC?CPh)]₂ · 2 CH₂Cl₂ and PPh₄[ReOCl₄] Single crystals of [ReCl₄(PhC?CPh)]₂ · 2 CH₂Cl₂ were obtained by chilling dilute solutions of the solvate [ReCl₄(PhC?CPh)POCl₃] in CH₂Cl₂. PPh₄[ReOCl₄] was formed by the reaction of the diphenyl acetylene complex [ReCl₅(PhC?CPh)] with PPh₄Cl · H₂O in CH₂Cl₂ solution. [ReCl₄(PhC?CPh)]₂ · 2 CH₂Cl₂: space group P2₁/c, Z = 2, 2244 observed independent reflexions, R = 0.038. Lattice parameters (19°C): a = 987.2 pm; b = 1533.9 pm; c = 1193.8 pm; β = 90.17° The compound forms centrosymmetrical dimeric molecules with ReCl₂Re bridges with Re? Cl distances of 241.2 and 267.6 pm. The longer Re? Cl bond is situated in trans-position to the equatorial, side-on coordinated diphenyl acetylene ligand with mean Re? C distances of 200 pm. PPh₄[ReOCl₄]: space group P4/n, Z = 2, 1487 observed, independent reflexions, R = 0.047. Lattice parameters (19°C): a = b = 1272.0 pm; c = 771.3 pm. The compound crystallizes in the AsPh₄[RuNCl₄] type; it consists of [ReOCl₄]^? anions and PPh₄⁺ cations. The anions are tetragonal with C_4v symmetry and bond lengths Re? O = 165.4 pm and Re? Cl = 232.6 pm; the bond angle OReCl is 106.7°.     

Darstellung und Schwingungsspektren der Komplexe [MBr6]−, [Br5MN3]− und [Br5MNPPh3]− von Niob und Tantal Die Kristallstruktur von PPh4[NbBr6]

Preparation and vibrational spectra of the complexes [MBr₆]^?, [Br₅MN₃]^? and [Br₅MNPPh₃]^? of niobium and tantalum. Cyrstal structure of PPh₄[NbBr₆] The compounds PPh₄[MBr₆] and PPh₄[MBr₅N₃] are obtained by reaction of MBr₅ with PPh₄Br or PPh₄N₃, respectively, in CH₂Cl₂ solution (M ? Nb, Ta). The azido complexes PPh₄[MBr₅N₃] can also be obtained by reactions of the hexabromo complexes with iodine azide. According to its i.r. spectrum the symmetry of the [MBr₆]^? ion is lower than O_h in the solide state. This is corfirmed for PPh₄[NbBr₆] by a crystal structure analysis; it crystallizes in the monoclinic space group B2/b with four formula units in the unit cell and with the lattice constants a = 2301, b = 1777, c = 686 pm and γ = 96,6°. The structure was determined with X-ray diffraction data and was refined to a residual index of R = 0.055. The [NbBr₆]^? ion has the symmetry C_i, the deviations from O_h being small. In the azido complexes [MBr₅N₃]^? the azido groups are covalently linked with the metal. From [NbBr₅N₃]^? and PPh₃ the complex [Br₅Nb?N?PPh₃]^?, is obtained; for the analogous formation of the corresponding Ta complex photochemical activation is necessary. In this way the complex [Cl₅Nb?N?AsPh₃]^? can also be obtained. I.r. spectra of all the compounds are reported and assigned.     

Thiobromokomplexe von Arsen und Antimon Darstellung und Kristallstrukturen von (PPh4)2[As2SBr6] · CH2Br2 und (PPh4)2[Sb2SBr6] · CH2Br2

Thiobromo Complexes of Arsenic and Antimony. Preparation and Crystal Structures of (PPh₄)₂[As₂SBr₆] · CH₂Br₂ and (PPh₄)₂[Sb₂SBr₆] · CH₂Br₂ (PPh₄)₂[As₂SBr₆] · CH₂Br₂ is formed by the reaction of As₂S₃, PPh₄I and HI in dibromomethane. It can also be obtained, as well as (PPh₄)₂[Sb₂SBr₆] · CH₂Br₂, from (PPh₄)₂[As₂Br₈] and (PPh₄)₃[Sb₂Br₉], respectively, with bistrimethylsilylsulfide. The crystal structures of the title compounds were determined by X-ray diffraction. They are isotypic with (PPh₄)₂[As₂SCl₆] · C₂H₄Cl₂. In the anions [M₂SBr₆]^2? the M atoms (As or Sb) have a distorted octahedral coordination, the two octahedra share acommon face with one bridging S and two Br atoms; the lone electron pairs occupy the trans positions to the S atom. Crystal data: triclinic, space group P1 , Z = 2; (PPh₄)₂[As₂SBr₆] · CH₂Br₂, a = 119.1, b = 1203.6, c = 2067.5 pm α= 94.89, β = 97.78, γ = 112.20°, 3046 independent observed reflexions, R = 0.083; (PPh₄)₂[Sb₂SBr₆] · CH₂Br₂, a = 1198.9, b = 1224.3, c = 2085.5pm, α = 95.04, β = 98.48, γ = 112.13°C, 2380 reflexions, R = 0.079.     

Die Bildung von PPh4[WOCl4 · THF] und PPh4Cl · 4As4S3 aus W(CO)6 und PPh4[As2SCl5] sowie ihre Kristallstrukturen

Formation of PPh₄[WOCl₄ · THF] and PPh₄Cl · 4As₄S₃ from W(CO)₆ and PPh₄[As₂SCl₅] and their Crystal Structures When W(CO)₆ and PPh₄[As₂SCl₅] are irradiated with UV light in tetrahydrofurane, PPh₄[WOCl₄ · THF], PPh₄ Cl· 4As₄S₃ and PPh₄[Cl₂H] are obtained. X-ray crystal structure determinations were performed. PPh₄[WOCl₄ · THF], monoclinic, space group P2₁/c, Z = 4, a = 1207.5(2), b = 1003.7(2), c = 2642.0(5) pm, β = 114.71(1)°, R = 0.049% for 2824 reflexions; PPh₄⁺ and [WOCl₄. THF]^? ions are present, the WOCl₄ group having the shape of a tetragonal Pyramid with a short W ? O bond (169 pm) and the THF molecule being weakly associated (W? O 236 pm). PPh₄Cl · 4AsS₃, tetragonal, I4₁/a, Z = 4, a = 1742.3(3), c = 1664.5(4) pm, R = 0.066% for 1350 reflexions; it consists of separate PPh₄⁺ and Cl^? ions and As₄S₃ 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.     

Spektroskopische und kristallographische Charakterisierung von [Cl3PNPCl3][MoOCl4] und die Kristallstruktur von [Cl3PNPCl3][MoCl6]

Spectroscopic and Crystallographic Characterization of [Cl₃PNPCl₃][MoOCl₄] and Crystal Structure of [Cl₃PNPCl₃][MoCl₆] [Cl₃PNPCl₃][MoCl₆] was obtained by reaction of MoCl₅ with [Cl₃PNPCl₃]Cl or [Cl₃PNPCl₃][PCl₆]. Its crystal was determined by X-ray diffraction (R = 0.072 for 889 observed reflexions). Lattice parameters: a = 811.9, b = 2086, c = 1016 pm, β = 101.7°, space group P2₁/c, Z = 4. The [Cl₃PNPCl₃]⁺ ions have a similar structure as in Cl₃PNPCl₃ [PCl₆] with PNP angles of 139°, but the crystal structures of the two compounds are not isotypic. Partial hydrolysis of [Cl₃PNPCl₃][MoCl₆] yields [Cl₃PNPCl₃][MoOCl₄] which forms green, very moisture sensitive crystals. X-ray diffraction patterns of [Cl₃PNPCl₃][MoOCl₄] single crystals exhibit planes of diffuse scattered radiation perpendicular to c^*, which show the presence of a two-dimensional disorder. Additional sharp reflexions correspond to an averaged structure with the lattice parameters a = 1598.4, b = 1141.2 and c = 415.1 pm, Z = 2, space group Pba2. Refinement of the averaged     

(PPh4)2[V2Cl9][VCl5] · CH2Cl2 Synthese,IR-Spektrum und Kristallstruktur

(PPh₄)₂[V₂Cl₉][VCl₅] · CH₂Cl₂. Synthesis, I.R. Spectrum, and Crystal Structure The title compound was obtained by addition of CCl₄ to a solution of PPh₄Cl and excess VCl₄ in CH₂Cl₂. It forms black crystals which are light and moisture sensitive. The i.r. spectrum is reported. The crystal structure was determined by X-ray diffraction (3044 independent reflexions, R = 0.063). Crystal data: triclinic, space group P1 , Z = 2, a = 1186, b 1325, c = 1995 pm, α 97.5, β 105.6°, γ 93.4°. The structure consists of PPh₄⁺ cations, V₂Cl₉? and VCl₅? anions and CH₂Cl₂ molecules. The V₂Cl₉? ions consist of face-sharing octahedra with a long V…?V distance of 333 pm; the VCl₅? ions form nearly ideal trigonal bipyramids with V? Cl bonds of 228 pm (axial) and 218 pm (equatorial). Both anions deviate only marginally from D_3h symmetry. Half of the cations is arranged to (PPh₄⁺)₂ pairs about inversion centers.     

Thiohalogeno-Verbindungen von Niob und Tantal: NbSCl3, TaSCl3, [NbSCl5]2−, [TaSCl5]2−, [NbSBr4]− Die Kristallstrukturen von (PPh4)2[NbSCl5] · 2 CH2Cl2 und NEt4[NbCl6]

Thiohalo Compounds of Niobium and Tantalum: NbSCl₃, TaSCl₃, [NbSCl₅]^2?, [TaSCl₅]^2?, [NbSBr₄]^?. Crystal Structures of (PPh₄)₂[NbSCl₅] · 2 CH₂Cl₂ and NEt₄[NbCl₆] NbSCl₃ can be obtained from NbCl₅ by reaction with H₂S or bistrimethylsilyl sulfide in a suspension of CCl₄ or CH₂Cl₂, respectively; in the latter case the product contains a rest of trimethylsilyl groups. This also applies for TaSCl₃, NbSBr₃ and TaSBr₃, which are formed from the metal pentahalides and S(SiMe₃)₂. NEt₄[NbSCl₄] is formed together with NEt₄[NbCl₆] in the reaction of NbCl₅ with NEt₄SH in CH₂Cl₂. PPh₄[NbCl₆] reacts with S(SiMe₃)₂ in dichloromethane yielding (PPh₄)₂[NbSCl₅] · 2 CH₂Cl₂, whereas PPh₄[NbSBr₄] is obtained from PPh₄[NbBr₆] and S(SiMe₃) under the same conditions. (PPh₄)₂[TaSCl₅] · 2 CH₂Cl₂ was obtained from TaSCl₃ and PPh₄Cl in CH₂Cl₂. According to an X-ray crystal structure determination (PPh₄)₂[NbSCl₅] · 2 CH₂Cl₂ crystallizes in the β-(AsPh₄)₂[UCl₆] · 2 CH₂Cl₂ type with positionally disordered, octahedral anions. Crystal data: a = 1 021.7, b = 1120.4, c = 1 243.3 pm, α = 70.77, β = 80.24, γ = 80.54°, space group P1 , Z = 2; 2462 unique observed reflexions, R = 0.036. NEt₄[NbCl₆] crystallizes isotypic to NEt₄[WCl₆], a = 723.5, b = 1 018.0, c = 1 174.6 pm, β = 100.07°, space group P2₁/n, Z = 2; 1 875 reflexions, R = 0.075.     

Nitrosylbromokomplexe des Rheniums: Re(NO)2Br3 und [Re(NO)2Br4]⊖; die Kristallstruktur von PPh4[Re(NO)2Br4] · 2 CCl4

Nitrosyl Bromo Complexes of Rhenium: Re(NO)₂Br₃ and [Re(NO)₂Br₄]^?; Crystal Structure of PPh₄[Re(NO)₂Br₄] · 2 CCl₄ PPh₄[Re(NO)₂Br₄] is prepared in the form of dark red-brown powder by the reaction of PPh₄[Re(NO)₂Cl₄] with excess boron tribromide. From a solution of CH₂Br₂ and CCl₄ it crystallizes with two moles CCl₄, one of which splits off easily in vacuo. The reaction of aluminum tribromide in CH₂Br₂ solution leads to a slightly soluble red-brown Re(NO)₂Br₃ powder. The i.r. spectra indicate cis positions of the covalently bound NO ligands in both complexes. Re(NO)₂Br₃ is dimeric via bromo bridges. The crystal structure determination of PPh₄[Re(NO)₂Br₄] · 2 CCl₄ was solved by X-ray diffraction methods at ? 115°C. The complex crystallizes in the monoclinic space group P2₁/c with four formula units per unit cell (4434 independent reflexions, R = 0.085). The unit cell dimensions are a = 1 092.3 pm, b = 2088.0 pm, c = 1 657.6 pm, β = 96.10°. The structure consists of P(C₆H₅)₄^? cations, [Re(NO)₂Br₄]^? anions and intercalated CCl₄ molecules. In the anion the NO groups are covalently bound to the Re atom like \documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {{\rm RE}}\limits^ \ominus = \mathop {\rm N}\limits^ \oplus = {\rm O} $\end{document} and they are arranged in cis position to one another.     

Investigation of Large Polychloride Anions: [Cl11]−, [Cl12]2−, and [Cl13]−

For decades the chemistry of polyhalides was dominated by polyiodides and more recently also by an increasing number of polybromides. However, apart from a few structures containing trichloride anions and a single report on an octachloride dianion, [Cl₈]^2?, polychlorine compounds such as polychloride anions are unknown. Herein, we report on the synthesis and investigation of large polychloride monoanions such as [Cl₁₁]^? found in [AsPh₄][Cl₁₁], [PPh₄][Cl₁₁], and [PNP][Cl₁₁]?Cl₂, and [Cl₁₃]^? obtained in [PNP][Cl₁₃]. The polychloride dianion [Cl₁₂]^2? has been obtained in [NMe₃Ph]₂[Cl₁₂]. The novel compounds have been thoroughly characterized by NMR spectroscopy, single‐crystal Raman spectroscopy, and single‐crystal X‐ray diffraction. The assignment of their spectra is supported by molecular and periodic solid‐state quantum‐chemical calculations.