Synthese und Kristallstruktur von (AsPh4)2[Cl5WNSNWCl5]

Synthesis and Crystal Structure of (AsPh₄)₂[Cl₅WNSNWCl₅] . The chlorothionitrene complex [WCl₄(NSCl)]₂ reacts with excess tetraphenylarsonium chloride via the intermediate AsPh₄[Cl₅W(NSCl)] to yield the title compound. This was characterized by its i.r. spectrum and an X-ray crystal structure determination (4078 reflexions uncluding Friedel pairs, R = 0.059). (AsPh₄)₂[Cl₅WNSNWCl₅] crystallizes in the monoclinic system, a = 1110.5, b = 1714.6, c = 1521.7 pm, β = 107.24°, Z = 2. The space group is either P2₁/n with anions statistically disordered in two different positions or Pn with an apparent higher symmetry due to the presence of inversion twins. Bond distances and angles correspond to the formula      

Cyclo-S2N2-verbrückte Chlorthionitrenkomplexe von Molybdän und Wolfram. Die Kristallstruktur von μ-(S2N2)[MoCl4(NSCl)]2

Cyclo-S₂N₂ Bridged Chlorothionitrene Complexes of Molybdenum and Tungsten. Crystal Structure of μ-(S₂N₂)[MoCl₄(NSCl)]₂ Molybdenum pentachloride reacts with (NSCl)₃ in CH₂Cl₂ suspension giving a product mixture from which the complex μ-(S₂N₂)[MoCl₄(NSCl)]₂ can be extracted with CH₂Cl₂. It forms black crystals, whereas the corresponding tungsten compound forms copper-red crystals. μ-(S₂N₂)[WCl₄(NSCl)]₂ is obtained by abstraction of SCl₂ and chlorine from N(SCl)₂[WCl₅(NSCl)], which can be obtained from WCl₆ and N₂S₃Cl₂. According to their i.r. spectra both complexes μ-(S₂N₂)[MCl₄(NSCl)]₂ have the same molecular structure. The crystal structure of μ-(S₂N₂)[MoCl₄(NSCl)]₂ was determined and refined with X-ray diffraction data (1851 reflexions, R = 0.019). It crystallizes in the triclinic space group P1 with two molecules per unit cell. The lattice constants are a = 685, b = 735, c = 963 pm, α = 76.6°, β = 80.9°, γ = 87.0°. μ-(S₂N₂)[MoCl₄(NSCl)]₂ forms centrosymmetric molecules in which the Mo atoms of the MoCl₄(NSCl) units are linked via the N atoms of a planar N₂S₂ ring. The Mo atoms have coordination number 6, having the N atom of the chlorothionitrene ligand Mo in trans position to the N atom of the S₂N₂ ring.     

Chlorthionitrenkomplexe des Rheniums Die Kristallstruktur von AsPh4[ReCl4(NSCl)2] · CH2Cl2

Chlorothionitrene Complexes of Rhenium. Crystal Structure of AsPh₄[ReCl₄(NSCl)₂] · CH₂Cl₂ Rhenium pentachloride reacts in POCl₃ solution with (NSCl)₃ forming the chlorothionitrene complexes [(Cl₃PO)ReCl₄(NSCl)] ( I ) and [(Cl₃PO)ReCl₃(NSCl)₂] ( II ). I reacts with AsPh₄Cl in CH₂Cl₂ solution under abstraction of SCl₂ and POCl₃, yielding AsPh₄[ReNCl₄], while II forms the complex AsPh₄[ReCl₄(NSCl)₂] · CH₂Cl₂. The i.r. spectra of the compounds are discussed and assigned. The crystal structure of AsPh₄[ReCl₄(NSCl)₂] · CH₂Cl₂ was determined and refined with X-ray diffraction data (R = 0.031 for 2785 reflexions). It crystallizes in the space group Pī with two formula units per unit cell; the lattice constants are a = 1119, b = 1144, c = 1473 pm, α = 77.6, β = 70.8 and γ = 71.2°. The two NSCl ligands have cis arrangement with nearly linear Re?N?S groups, with interatomic distances corresponding to double bonds. The Re? Cl bonds are somewhat longer than usual and show no trans-effect; this is possibly due to Cl…?H? C bridges.     

Thionitrosylkomplexe des Osmiums. Die Kristallstruktur von AsPh4[OsCl4(NS)2Cl]

Thionitrosyl Complexes of Osmium. Crystal Structure of AsPh₄[OsCl₄(NS)₂Cl] The reaction of osmium pentachloride with trithiazyl chloride (NSCl)₃ yields the thiazylchloride complex [OsCl₄(NSCl)₂], from which the thionitrosyl complex AsPh₄[OsCl₄(NS)₂Cl] is obtained by reaction with AsPh₄Cl in CH₂Cl₂. From this, the neutral thionitrosyl complex [OsCl₄(NS)₂] forms by chloride abstraction with gallium trichloride. The crystal structure of AsPh₄[OsCl₄(NS)₂Cl] was determined and refined with the aid of X-ray diffraction data (R = 0.033, 2161 reflexions). It crystallizes in the monoclinic space group P2₁/c with four formula units per unit cell. The lattice constants are a = 1735, b = 1058, c = 1578 pm and β 95.64°. In the [OsCl₄(NS)₂Cl]^? ion the osmium is octahedrally coordinated by four Cl atoms and two NS groups in a cis arrangement. The NS groups are essentially linear with the bond lengths Os?N 184 pm and N?S 146 pm. Loosely attached to one of the S atoms there is a Cl atom (S? Cl distance 228 pm); in the crystal it statistically belongs to both S atoms with an occupation probability of one half, and it cannot be decided whether there is a dynamical fluctuation between the S atoms or a static positional disorder. However, according to the i.r. spectrum the dynamical model seems more probable.     

Funktionalisierte Alkinkomplexe von Wolfram(VI). Synthese und Kristallstrukturen von [WCl4(Et?Se?CC?Se?Et)(THF)] und [WCl4(Et?Te?CC?Te?Et)(THF)]

Functionalized Alkyne Complexes of Tungsten(VI). Syntheses and Crystal Structures of [WCl₄(Et? Se? C?C? Se? Et)(THF)] and [WCl₄(Et? Te? C?C? Te? Et)(THF)] The title compounds have been prepared by reactions of [WCl₄(SEt₂)₂] with the alkynes Et? X? C?C? X? Et (X = Se, Te) in CCl₄ solution and subsequent addition of tetrahydrofurane. Both complexes were characterized by crystal structure determinations. [WCl₄(Et? Se? C?C? Se? Et)(THF)]: Space group P2₁/n, Z = 4, structure determination with 2942 unique reflections, R = 0.038. Lattice dimensions at 20°C: a = 934.2, b = 1639.5, c = 1189.5 pm, β = 96.497°. [WCl₄(Et? Te? C?C? Te? Et)(THF)]: Space group P2₁/n, Z = 4, structure determination with 4097 unique reflections, R = 0.067, Lattice dimensions at ?70°C: a = 899.2, b = 1691.9, c = 1213.3 pm, β = 96.82°. The complexes have monomeric molecular structures with the oxygen atom of the THF molecules in trans-position to the side-on bound alkyne ligands.     

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°.     

[WCl4(Me3Si?CC?SiMe3)]2 Synthese,IR-Spektrum und Kristallstruktur

[WCl₄(Me₃Si? C?C? SiMe₃)]₂. Synthesis, I.R. Spectrum, and Crystal Structure The title compound is obtained from tungsten hexachloride and bis-trimethylsilyl acetylene in the presence of C₂Cl₄ in dichloro methane, forming green crystals. The complex is characterized by the mass spectrum, the i.r. spectrum, and by a structural analysis with the aid of X-ray diffraction data. [WCl₄(Me₃Si? C?C? SiMe₃)]₂ crystallizes triclinic in the space group P1 with one dimeric formula unit per unit cell (2 231 observed, independent reflexions, R = 4.6%). The cell dimensions are a = 928, b = 938, c = 1 080 pm; α = 115.3°, β = 91.9°, γ = 100.0°. The complex forms centrosymmetric dimers, the units being linked by chloro bridges of bond lengths W? Cl 244 and 272 pm. The trans-position to the long W? Cl bridge is occupied by the acetylene ligand which is bonded side-on with identical W? C bond lengths of 203 pm. Together with the three terminal chlorine ligands (mean W? Cl distance 231 pm) the tungsten atom achieves coordination number seven.     

[ReCl3(NSCl)2(CH3CN)]. Synthese,IR-Spektrum und Kristallstruktur

[ReCl₃(NSCl)₂(CH₃CN)]. Synthesis, I. R. Spectrum, and Crystal Structure Black, moisture sensitive crystals of the title compound are obtained from [ReCl₃(NSCl)₂]₂ and acetonitrile in dichloromethane. The complex is characterized by its i.r. spectrum and an X-ray crystal structure determination (2483 observed independent reflexions, R = 0.035). Crystal data: triclinic, space group P1 , Z = 2, a = 681.8, b = 899.9, c = 1104.0 pm, α = 110.50, β = 97.90 and γ = 101.34°. In the monomeric [ReCl₃(NSCl)₂(CH₃CN)] molecule the Re atom has a distorted octahedral coordination with meridional arrangement of the Cl atoms. The chlorothionitrene ligands have nearly linear ReNS groups with bond lengths that correspond to double bonds (ReN 178 and 179 pm); this agrees with the NReN bond angle of 100°.     

Diiodacetylenkomplexe von Wolfram(IV). Die Kristallstruktur von PPh4[WCl5(C2l2)] · 0,5 CH2Cl2

Diiodoacetylene Complexes of Tungsten(IV). Crystal Structure of PPh₄[WCl₅(C₂I₂)] · 0.5 CH₂Cl₂ Tungsten hexachloride and diiodoacetylene react in CCl₄ solution forming [WCl₄(I? C?C? I)]₂ which has a dimer structure with chloro bridges. In CH₂Cl₂, it reacts with PPh₄Cl yielding PPh₄[WCl₅(I? C?C? I)] · 0.5 CH₂Cl₂. In both compounds the C₂I₂ ligands attain a marked increase in thermal stability by their side-one coordination to the tungsten atoms. The crystal structure of the PPh₄^⊕ salt was determined with X-ray diffraction data (3879 observed reflexions, R = 0.050). PPh₄[WCl₅(C₂I₂)] · 0.5 CH₂Cl₂ crystallizes in the space group P2₁/n with 8 formula units per unit cell. The lattice constants are a = 1723.0, b = 1681.2, c = 2214.6 pm and β = 94.38°. There are two crystallographically independent [WCl₅(C₂I₂)]^? ions which differ only slightly from one another. The C₂I₂ ligand has a staggered arrangement relative to the W? Cl groups, with C? C bond lengths of 127 pm. The infrared spectra are discussed.     

N(SCl)2 ⊕[MoCl5(NSCl)]⊖, ein Chlorthionitrenokomplex von Molybdän(VI)

N(SCl)₂^⊕ [MoCl₅(NSCl)]^?, a Chlorothionitrene Complex of Molybdenum (VI) . The title compound is formed together with MoCl₃(N₃S₂) by the reaction of MoCl₄ or MoCl₅ with (NSCl)₃ in CH₂Cl₂. The black, crystalline compound was characterized by its i.r. spectrum and an X-ray crystal structure determination. N(SCl)₂^⊕[MoCl₅(NSCl)]^? crystallizes in the monoclinic space group P2₁/n with four formula units per unit cell. The lattice constants are a = 716.3, b = 1627.4, c = 1178.9 pm and β = 100.90°. The [MoCl₅(NSCl)]^? ion posseses an almost linear Mo = N = S grouping with bond lengths that can be interpreted as double bonds. Crystal data for AsPh₄[MoCl₅(NSCl)] are reported.     

Dichloracetylen als stabiler Komplexligand Die Kristallstruktur von PPh4[WCl5(C2Cl2)] · 0,5 CCl4

Dichloro Acetylene as Complex Ligand. Crystal Structure of PPh₄[WCl₅(C₂Cl₂)] · 0.5 CCl₄ Tungsten hexachloride and dichloro acetylenediethyletherate react in boiling CCl₄ in presence of C₂Cl₄ as reducing agent forming [Et₂O · WCl₄(C₂Cl₂)]. In vacuo the complex looses ether giving the dichloro acetylene complex [WCl₄(C₂Cl₂)]₂ which is dimeric with chloro bridges. Both complexes react with tetraphenylphosphonium chloride to form PPh₄[WCl₅(C₂Cl₂)] which is equally prepared by ligand exchange of PPh₄[WCl₅(C₂I₂)] with silver chloride. All dichloro acetylene complexes are red to brown crystalline solids sensitive to moisture, and are thermally and mechanically very stable compared with the highly explosive dichloro acetylene. The compounds are characterized by their i.r. spectra; [Et₂O · WCl₄(C₂Cl₂)] was additionally investigated by ¹³C-nmr spectroscopy. PPh₄[WCl₅(C₂Cl₂)] · 0.5 CCl₄ formes dark brown crystals; according to the structural investigation by X-ray diffraction methods the compound crystallizes orthorhombic in the space group Pbca with 8 formula units per unit cell (1317 observed, independent reflexions, R = 0.049). The cell dimensions are a = 1702 pm, b = 1675 pm and c = 2228 pm. The compound consists of [WCl₅(C₂Cl₂)]? anions and PPh₄⊕ cations including CCl₄ molecules without bonding interactions. The tungsten atoms are seven-coordinated by five chlorine atoms and two carbon atoms. The dichloro acetylene ligand is bonded symmetrically side-on and has a C? C bond length of 128 pm. The W? C distances are 201 pm, the four equatorial Cl atoms have W? Cl bond lengths of 234 pm whereas the chlorine atom in trans-position to the W? C₂ group is situated in a distance of 244 pm.     

Bis[(tert-butylnitren)tetrachlorowolfram] Synthese,IR-Spektrum und Kristallstruktur

Bis[(tert-butylnitrene)tetrachlorotungsten]: Synthesis, I.R. Spectrum, and Crystal Structure The title compound, forming red crystals, is prepared by the reaction of tungsten hexachloride with the iminoborane Me₃CB?NCMe₃. With PPh₄Cl it forms the chloro complex PPh₄[WCl₅(NCMe₃)]. Both complexes are characterized by their i.r. spectra. The crystal structure of [WCl₄(NCMe₃)]₂ was determined by the aid of X-ray diffraction (space group P2₁/c, Z = 2 dimeric units, 1938 independent, observed reflexions, R = 0.028, a = 636, b = 1537, c = 1124 pm; β 104.74°). The compound forms centrosymmetric molecules in which the tungsten atoms are bridged via chloro atoms with W? Cl bond lengths of 241 and 275 pm. In position trans to the longer WCl bond the nitrene ligand is attached with a WN distance of 170 pm which corresponds to a triple bond; the W?N? C bond angle is 173°.     

Diphenylacetylen-Komplexe von Niob,Molybdän,Wolfram und Rhenium Die Kristallstruktur von [NbCl3(Ph?CC?Ph)]4

Diphenylacetylene Complexes of Niobium, Molybdenum, Tungsten, and Rhenium. Crystal Structure of [NbCl₃(Ph? C?C? Ph)]₄ Syntheses and i.r. spectra of the following diphenylacetylene complexes are reported: The chloro complexes 1, 2, 4, 7 and 8 are formed in the pentachlorides of niobium, molybdenum, rhenium, and tungsten hexachloride, respectively, with diphenyl acetylene. The bromo and iodo complexes 3, 5 and 6 are obtained by halogen exchange with boron halides, and the derivatives 9, 10 and 11 are obtained by reactions of PPh₄Cl or AsPh₄Cl and PPh₃ with the corresponding starting materials. The crystal structure of 1 was determined by the aid of X-ray diffraction data (R = 5.9% for 1548 independent, observed reflexions). The complex crystallizes triclinic in the space group P1 with one tetrameric molecule [NbCl₃(Ph? C?C? Ph)]₄ per unit cell. The cell dimensions at 20°C are a = 1074 pm, b = 1390 pm, c = 1299 pm, α = 104.3°, β = 108.0°, γ = 108.7°. 1 occurs as a centrosymmetric tetramer, which can be regarded as a distorted double hexahedron with two corners missing. Association is effected by chloro bridges in which the chlorine atoms have coordination number two and three. The diphenylacetylene ligands are bonded to the niobium atoms side-on with almost equal Nb? C bond lengths of average value 205 pm. Thus the Nb atoms achieve coordination number seven.     

Synthese und Kristallstrukturen der Wolfram(VI)-Alkin-Komplexe [W2(O)(OMe)6(Et?Se?CC?Se?Et)2] und Li[W(OMe)5(Et?Te?CC?Te?Et)]

Synthesis and Crystal Structures of the Tungsten(VI)-alkyne Complexes [W₂(O)(OMe)₆(Et? Se? C?C? Se? Et)₂] and Li[W(OMe)₅(Et? Te? C?C? Te? Et)] The title compounds have been prepared by reactions of lithium methanolate with [WCl₄(Et? Se? C?C? Se? Et)(THF)] and [WCl₄(Et? Te? C?C? Te? Et)(THF)], respectively, in diethylether suspensions. Both complexes were characterized by crystal structure determinations. [W₂(O)(OMe)₆(Et? Se? C?C? Se? Et)₂]: Space group P1 , Z = 2, structure determination with 4 320 observed unique reflections, R = 0.041. Lattice dimensions at ?70°C: a = 949.3, b = 1 225.3, c = 1 285.0 pm, α = 82.48°; γ = 82.44°; β = 81.44°. The tungsten atoms are bridged by three μ₂-O-atoms of the OMe groups; the alkyne ligands are coordinated side-on in a metallacyclopropene-like fashion. Li[W(OMe)₅(Et? Te? C?C? Te? Et)]: Space group P1 , Z = 2, structure determination with 9 381 observed unique reflections, R = 0.038. Lattice dimensions at ?70°C: a = 983.4, b = 1606.9, c = 1971.5 pm, α = 66.09°, β = 84.29°, γ = 79.83°. The lithium ions link the [W(OMe)₅(Et? Te? C?C? Te? Et)]^? anions to a trimeric ion ensemble via the O atoms of three OMe groups of each anion.     

S4N3⊕[ReCl4(NSCl)2]⊖ Synthese und Kristallstruktur

S₄N₃^⊕[ReCl₄(NSCl)₂]^?. Synthesis and Crystal Structure S₄N₃^⊕[ReCl₄(NSCl)₂]^? is formed as a byproduct in the reaction of Re₂(CO)₁₀ with excess trithiazyl chloride. The compound is characterized by a crystal structure analysis by X-ray methods. S₄N₃[ReCl₄(NSCl)₂] crystallizes in the noncentrosymmetric space group P2₁2₁2₁ with four formula units per unit cell and the lattice dimensions a = 980, b = 1205, c = 1362 pm (2376 observed, independent reflexions; R = 0.076). The compound consists of the well known cyclic planar S₄N₃^⊕-cations and anions [ReCl₄(NSCl)₂]^?, in which the rhenium atom is coordinated octahedral by four Cl atoms and two cis-positioned NSCl ligands. The mean Re? N and N? S bond lengths (177 pm and 158 pm) correspond to double bonds. The bond lengths and angles are much like in the structure of AsPh₄[ReCl₄(NSCl)₂]; however the chlorine atoms of the NSCl ligands are turned to each other.     

Bromthionitren-tetrabromo-wolfram, [WBr4(NSBr)]2

Bromothionitrene-tetrabromo-tungsten, [WBr₄(NSBr)]₂ [WBr₄(NSBr)]₂ is prepared by the reaction of the corresponding chlorothionitrene complex [WCl₄(NSCl)]₂ with excess trimethylsilylbromide. Unpure [WCl₄(NSBr)]₂ was also prepared. According to the i.r. spectra the bromothionitrene complexes are similar to the chlorothionitrene complex [WCl₄(NSCl)]₂, which was characterized earlier by X-ray methods. [MoCl₄(NSCl)]₂ reacts with Me₃SiBr forming MoNBr₃.     

Chalkogen‐Derivate der Halbsandwich‐Wolfram(V)‐Komplexe Cp*WCl4 und Cp*WCl4(PMe3). Röntgen‐Kristallstrukturanalysen von anti‐[Cp*W(Se)(μ‐Se)]2 und Cp*W(S)2(OMe)

Chalcogen Derivatives of the Halfsandwich Tungsten(V) Complexes Cp*WCl₄ and Cp*WCl₄(PMe₃). X‐Ray Crystal Structure Analyses of anti ‐[Cp*W(Se)(μ‐Se)]₂ and Cp*W(S)₂(OMe) The chalcogenation of Cp*WCl₄ ( 1 ) by E(SiMe₃)₂ (E = S, Se) and Te(SiMe₂^tBu)₂ in chloroform solution leads to dimeric products of the type anti‐[Cp*W(E)(μ‐E)]₂ (E = S ( 3 a ), Se ( 3 b ) and Te ( 3 c )). An X‐ray structure determination of 3 b indicates a centrosymmetric molecule containing a planar W(μ‐Se)₂W ring, the W–W distance (297.9(1) pm) corresponds to a single bond. In the presence of air the two terminal chalcogenido ligands (E) in 3 a – c are stepwise replaced by oxido ligands (O) to give [Cp*W(O)(μ‐E)]₂ (E = S ( 5 a ), Se ( 5 b ) and Te ( 5 c )) in quantitative yields. The reaction of Cp*WCl₄ with H₂S or ammonium polysulfide, (NH₄)₂S_x (x ∼ 10), leads to Cp*W(S)₂Cl ( 6 a ); the corresponding methoxy derivative, Cp*W(S)₂OCH₃ ( 9 a ), has been characterized by an X‐ray structure analysis. On the other hand, the reaction of Cp*WCl₄(PMe₃) ( 2 ) with sodium tetrasulfide, Na₂S₄, in dimethylformamide solution gives a mixture of mononuclear Cp*W(S)(S₂)Cl ( 8 a ), dinuclear [Cp*W(S)(μ‐S)]₂ ( 3 a ) and a trinuclear side‐product of composition Cp*₂W₃S₇ ( 13 a ). Terminal sulfido ligands are replaced by terminal oxido ligands in solution in the presence of oxygen. Thus, 6 a is stepwise converted into Cp*W(O)(S)Cl ( 10 a ) and CpW(O)₂Cl ( 12 a ), whereas 8 a gives Cp*W(O)(S₂)Cl ( 11 a ) and 13 a leads to Cp*₂W₃(O)S₆ ( 14 a ). The disulfido complexes 8 a and 11 a are desulfurized by triphenylphosphane to give 6 a and 10 a . The new complexes have been characterized by their IR and NMR spectra and by mass spectrometry.     

Synthese,IR-Spektrum und Kristallstruktur von PPh4[OsCl4(NO)(NSCl)]

Synthesis, I.R. Spectrum, and Crystal Structure of PPh₄[OsCl₄(NO)(NSCl)] Molten trithiazyl chloride reacts with OsCl₃(NO) to yield a product mixture consisting mainly of S₄N₃[OsCl₄(NO)(NSCl)] and S₄N₃Cl. Extraction of this mixture with a solution of tetraphenylphosphonium chloride in dichloromethane affords green (PPh₄)₂[OsCl₅(NO)] · 2 CH₂Cl₂ and the red title compound. PPh₄[OsCl₄(NO)(NSCl)] was characterized by its IR spectrum and an X-ray crystal structure analysis (3001 independent observed reflexions, R = 0.048). Crystal data: monoclinic, space group P2₁/c, Z = 4, a = 1716, b = 1054, c = 1588 pm, β = 96.25°. The compound consists of PPh₄⊕ cations and [OsCl₄(NO)(NSCl)]? anions in which the nitrosyl and the chlorothionitrene ligands have a cis arrangement. Due to positional disorder the NO and NSCl groups are superimposed statistically in the structure model.     

W2Cl7(CCl), a Polymeric Tungsten Chlorocarbyne Complex

Black crystals of W₂Cl₇(CCl) were obtained from the reaction of WCl₆ and As in CCl₄ at 250 °C under solvothermal conditions. The crystal structure (orthorhombic, space group Pbca, a = 1196(1), b = 1215.6(7), c = 1584(1) pm, Z = 8) is built of infinite zig‐zag chains of dinuclear complexes connected via bridging Cl atoms. The individual complexes are face‐sharing double octahedra concatenated via bridging Cl ligands. Each W atom is in a distorted octahedral coordination environment of five Cl atoms an the carbon atom of the μ₂ bridging chloromethylidyne ligand leading to the formula [{Cl₂W(μ‐CCl)(μ₂‐Cl)₂WCl₂}(μ‐Cl)]_n. The short W‐W distance of 256 pm indicates a multiple W‐W bond, the W‐C bonds of 195 pm are in the typical range for μ₂‐alkylidyne ligands, the C‐Cl bond of 167 pm is consistent with a sp¹ hybridisation on the carbon atom.     

[ReCl2(NS)(NSCl)(Pyridin)2], ein Thionitrosyl-chlorthio-nitrenkomplex des Rheniums

[ReCl₂(NS)(NSCl)(Pyridine)₂], a Thionitrosyl-chlorothionitrene Complex of Rhenium The title compound was obtained by the reaction of pyridine with either [ReCl₃(NSCl)₂POCl₃] or [ReCl₃(NSCl)₂]₂ · (μ-N₂S₂) under the reducing action of dichloromethane. It is slightly soluble in CH₂Cl₂, from which it can be obtained in form of black crystals. The IR spectrum is reported. The crystal structure of [ReCl₂(NS)(NSCl)(Pyridine)₂] was determined by X-ray diffraction (R = 0.027 for 2105 observed reflexions). Crystal data: a = 1551.6, b = 694.9, c = 1513.2 pm, β = 96.50°, space group P2₁/c, Z = 4. In the monomer molecules, each rhenium atom has a distorted octahedral coordination of two cis-chlorine atoms, two cis-nitrogen atoms of the pyridine ligands and two cis-nitrogen atoms of the thionitrosyl and chloro thionitrene ligands. One of the pyridine groups is in trans position to the nearly linear thionitrosyl group (angle ReNS 176°) with distances ReN of 177 pm and NS of 152 pm. However, in the trans position of the chlorothionitrene group (angle ReNS 159°, distances ReN 189 pm, NS 149 pm) a chlorine atom is found.