Dichlorphosphato-Komplexe von Zinn,Titan und Molybdän Die Kristallstruktur von (AsPh4)2[MoOCl3(PO2Cl2)]2

Dichlorophosphato Complexes of Tin, Titanium, and Molybdenum. Crystal Structure of (AsPh₄)₂[MoOCl₃(PO₂Cl₂)]₂ The dichlorophosphate complexes (AsPh₄)₂[SnCl₄(PO₂Cl₂)]₂ ( I ), (AsPh₄)₂[TiCl₄(PO₂Cl₂)]₂ ( II ) and (AsPh₄)₂[MoOCl₃(PO₂Cl₂)]₂ ( III ) are prepared by the reactions of SnCl₄, TiCl₄, and MoCl₅, respectively, with AsPh₄[PO₂Cl₂] in dichlormethan solutions. According to their i.r. spectra, the complex anions form dimeric species via the oxygen atoms of the dichlorophosphate groups; the ¹¹⁹Sn Mössbauer spectra of I are reported in addition. The crystal structure of III is solved by X-ray diffraction methods and refined to R = 4.3%. (AsPh₄)₂[MoOCl₃(PO₂Cl₂)]₂ crystallizes in the triclinic space group P1 with one formula unit pro unit cell. The structure consists of tetraphenylarsonium cations and centrosymmetric anions [MoOCl₃(PO₂Cl₂)]₂^2?. The molybdenum atoms of the anions are linked via the O atoms of the dichlorophosphate groups forming nonplanar Mo₂O₄P₂ eight-membered rings.     

Nitrosyl-tetrachloro-dichlorphosphato-molybdat(+II); Darstellung,IR-Spektrum und Kristallstruktur von (AsPh4)2[Mo(NO)Cl4(O2PCl2)]

Nitrosyl-tetrachloro-dichlorophosphate-molybdate(+II); Preparation, I.R. Spectrum and Crystal Structure of (AsPh₄)₂[Mo(NO)Cl₄(O₂PCl₂)] The title compound is prepared by the reaction of AsPh₄[Mo(NO)Cl₄] with AsPh₄? [PO₂Cl₂] in dichloromethane solution. It forms orange crystals which are only little sensitive to moisture. The complex crystallizes triclinic in the space group P1 with two formula units in the unit cell. The structure was solved by X-ray diffraction methods (2498 observed, independent reflexions, R = 5.4%). The compound consists of AsPh₄^⊕ cations and [Mo(NO)Cl₄(PO₂Cl₂)]^2? anions. The NO ligand is coordinated in linear array \documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {{\rm MO}}\limits^ \ominus = \mathop {\rm N}\limits^ \oplus = {\rm O}(177^{\circ}) $\end{document}. The dichlorophosphate group is coordinated in trans position to the NO ligand with one of its oxygen atoms. The Mo?N bonding of the NO ligand causes the bond angle NMoCl of 93.2° in average. The IR spectrum is recorded and assigned.     

CPh3⊕[Ph3CNWCl4(μ-F)WNCl2(μ-F)Cl4WNCPh3]⊖; Synthese und Kristallstruktur eines dreikernigen Nitrido-Nitren-Komplexes des Wolframs

CPh₃^⊕[Ph₃CNWCl₄(μ-F)WNCl₂(μ-F)Cl₄WNCPh₃]^?; Synthesis and Crystal Structure of a Trinuclear Nitrido Nitrene Complex of Tungsten Dark red crystals of the title compound are formed in the reaction of triphenyl carbonium tetrafluoro borate with AsPh₄[WNCl₄] in dichloro methane. They are characterized by a structural analysis by the aid of X-ray diffractional data as well as by it's IR spectrum. The complex crystallizes in the space group P_mmm with two formula units per unit cell. The cell dimensions are a = 2307, b = 1330 and c = 968 pm. Intensity measurements were carried out with 2 255 reflexions. Because of a disorder of the phenyl groups the structural parameters could only be refined to a final R-value of 9.3%. The structure consists of triphenyl carbonium cations and trinuclear anions [WNF₂Cl₂(Cl₄WNCPh₃)₂]^?. The anion can be regarded as a distorded trigonal-bipyramidal ion [WNF₂Cl₂]^?, coordinating to two molecules of Cl₄W?N? CPh₃ in trans-position to the nitrene ligands via W? F…?W bonds with different bond lengths.     

Studies on transition-metal nitrido and oxo complexes. Part VII(1). Substituted nitrido complexes of osmium and ruthenium

Summary Addition reactions of [MNCl₄]^– (M = Os or Ru) with ligands L or L to give [MNCl₄ · L]^– or [(MNCl₄)₂L]^2– (L = pyridine, pyridine-N-oxide,iso-quinoline or DMSO; L = hexamethylenetetramine, pyrazine or dioxan) are described. With NCO^–, [OsNCl₅]^– gives [OsN(NCO)₅]^2– but NCS^– gives a thionitrosyl complex, [Os(NS)(NCS)₅]^2–. Reactions of OsNCl₃(AsPh₃)₂ with pyridine, 1,10-phenanthroline and tertiary phosphites and phosphinites have been studied, as have reactions of triphenylphosphine with OsOCl₄ andtrans- [MO₂Cl₄]^2– (M = Os or Ru). The nitrido-iodo complexes [OsNI₄]^– and OsNI₃, (SbPh₃)₂ are also reported.     

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.     

Die Kristallstruktur von (AsPh4)2[W2NCl10]

Crystal Structure of (AsPh₄)₂[W₂NCl₁₀] The title compound is formed by a slow reaction of AsPh₄[WNCl₄] in acetonitrile solution in form of dark brown crystals. The crystal structure was solved by X-ray diffraction methods (R = 4.7%; 1461 observed, independent reflexions). (AsPh₄)₂[W₂NCl₁₀] crystallizes in the monoclinic space group P2₁/n with two formula units per unit cell. The structure consists of AsPh₄^θ and [W₂NCl₁₀]^2θ ions. The tungsten atoms with oxidation numbers five and six respectively, are linked by a linear, asymmetric nitrido bridge (r WN = 171 and 203 pm). The trans-effect of the W? N-multiple bonds causes a significant difference between axial (W? Cl_ax 243 pm) and equatorial (mean W? Cl_eq 230 pm) bond lengths.     

Nitrosylkomplexe des Molybdän(+II) Die Kristallstrukturen von [Mo(NO)Cl3 · POCl3]2 und von [AsPh4]2[Mo(NO)Cl5] · 2 CH2Cl2

Nitrosyl Complexes of Molybdenum (+II). Crystal Structures of [Mo(NO)Cl₃ · POCl₃]₂ and [AsPh₄]₂[Mo(NO)Cl₅] · 2 CH₂Cl₂ Solutions of MoCl₅ in POCl₃ react with NOCl forming the nitrosyl compound Mo(NO)Cl₃ · 2POCl₃ ( I ), which in CH₂Cl₂ cleaves off one solvate molecule, yielding the dimeric complex [Mo(NO)Cl₃ · POCl₃]₂ ( II ). Reaction with AsPh₄Cl in dichloro methane leads to the nitrosyl complexes AsPh₄[Mo(NO)Cl₄] · CH₂Cl₂ ( III ) and [AsPh₄]₂[Mo(NO)Cl₅] · 2CH₂Cl₂ ( IV ), respectively. The i.r. spectra are recorded and assigned. [Mo(NO)Cl₃ · POCl₃]₂ crystallizes monoclinic in the space group P2₁/c with two dimeric units per unit cell. The crystal structure was determined by X-ray diffraction methods (R = 0.040; 1391 observed, independent reflexions). Complex II is linked by chlorine bridges, forming a dimeric, centrosymmetric molecule of symmetry C_i. The N? O bond of the nitrosyl ligand is extremely short (108 pm), the Mo? N bond (181 pm) corresponds to a double bond. In trans position to the NO ligand, which is coordinated in linear array, there is the O atom of the solvate molecule POCl₃. [AsPh₄]₂[Mo(NO)Cl₅] · 2 CH₂Cl₂ crystallizes triclinic in the space group P1 with two units per unit cell (R = 0.039; 1967 observed, independent reflexions). The molybdenum atom is coordinated octahedrally by five Cl ligands and a nitrosyl group, as well coordinated in linear array (Mo? N? O 174°). The nitrosyl ligand exerts a significant trans-effect (r Mo? Cl_(trans) = 247 pm, r MoCl_4(eq)(average) = 239 pm).     

Strukturuntersuchungen an SIVN3-Gruppierungen. IV [1-3]

N-chloralkyl-nitridochloro Complexes of Molybdenum (VI). [Cl₅MoN-R]⁻ with R = CCl₃, C₂Cl₅. Crystal Structure of (AsPh₄)₂[(MoOCl₄)₂CH₃CN] In the reaction of tetraphenyl arsonium chloride with the complexes Cl₃PO (Cl₄)-MoN R (R=CCl₃, C₂Cl₅) the POCl₃ is displaced by chloride and yields [Cl₅MoN R] ⁻. From the i.r. spectra a structure with six-coordinated molybdenum and a MoN triple bond can be deduced. By reaction with water in acetonitrile the molybdenum is reduced to Mo(V) and the nitride ligand is removed yielding (AsPh₄)₂[(MoOCl₄)₂CH₃CN]. The crystal structure of this compund was determined with X-ray diffraction data. In the tetragonal structure (space group P4/n) AsPh₄⁺ cations and two different anions were found: square pyramidal [MoOCl₄]⁻ and [MoOCl₄ · NCCH₃]⁻ in which the nitrile is bonded in trans position to the oxygen. The short Mo O distances of 165 pm indicate a strong π-bonding.     

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.     

RhIAr/AuIAr′ Transmetalation: A Case of Group Exchange Pivoting on the Formation of M−M′ Bonds through Oxidative Insertion

By combining kinetic experiments, theoretical calculations, and microkinetic modeling, we show that Pf/Rf (C₆F₅/C₆Cl₂F₃) exchange between [AuPf(AsPh₃)] and trans‐[RhRf(CO)(AsPh₃)₂] does not occur by typical concerted Pf/Rf transmetalation via electron‐deficient double bridges. Instead, it involves asymmetric oxidative insertion of the Rh^I complex into the (Ph₃As)Au?Pf bond to produce a [(Ph₃As)Au?RhPfRf(CO)(AsPh₃)₂] intermediate, followed by isomerization and reductive elimination of [AuRf(AsPh₃)]. Interesting differences were found between the LAu?Ar asymmetric oxidative insertion and the classical oxidative addition process of H₂ to Vaska complexes.     

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.     

(AsPh4)2[(μ-N2S2) (VCI5)2] Synthese,IR-Spektrum und Kristallstruktur

(AsPh₄)₂[(μ-N₂S₂)(VCl₅)₂]. Synthesis, I.R. Spectrum, and Crystal Structure From the reaction of VCl₄ and S₃N₂Cl₂ in CCl₄ solution a solid, black product mixture is obtained. From this, the title compound can be extracted by reaction with AsPh₄Cl in CH₂Cl₂ solution. It can also be synthesized from AsPh₄VCl₅ and S₃N₃Cl₃ in CH₂Cl₂ solution. The i.r. spectra of (AsPh₄)₂[(μ-N₂S₂)(VCl₅)₂] (black crystal plates) and AsPh₄VCl₅ (brown needles) are reported. The crystal structure of (AsPh₄)₂[(μ-N₂S₂)(VCl₅)₂] was determined by X-ray diffraction. It crystallizes in the monoclinic space group P2₁/c with two formula units per unit cell. The lattice constants are a = 1113.9, b = 1712.8, c = 1508.8 pm, β = 106.68°. The centrosymmetric [(μ-N₂S₂)(VCl₅)₂]^2? ion consists of two quadratic-pyramidal VCl₅ units which are linked via the N atoms of a N₂S₂ ring. The N₂S₂ ring shows positional disorder in two different orientations in the crystal. The AsPh₄⊕ ions form (AsPh₄⊕)₂ pairs via inversion centers, each pair is surrounded by eight anions.     

Extraction of rhodium and iridium with 4-(non-5-yl) pyridine

The extraction of rhodium and iridium with 4-(non-5-yl)pyridine (NP) was investigated. The rate of rhodium extraction increases with increasing concentration of NP and chloride ions. Spectroscopic studies indicate that the extracted species is an ion pair, RhCl^3?₆ 3HNP⁺. Under the conditions of optimum Rh extraction ([Cl^?]=3.7 M, [NP]=0.3 M, [H]=0.08 M), iridium is also extracted by NP with similar efficiency in the form of IrCl^3?₆ 3HNP⁺. The use of hypophosphorous acid to labilize rhodium results in a better extraction of rhodium without significantly changing the extraction of iridium. The efficiency and kinetics of the rhodium extraction improve with increasing chloride concentration. For [Cl^?] ? 3.7 M, [H₃PO₂]=2.5 M, [NP]=0.3 M and Ph ≈ 1.6, 82% of rhodium is extracted in 4 min and 95% in 30 min.     

Interactions between silica particles and poly(2-vinylpyridine) brushes in aqueous solutions of monovalent and multivalent salts

AFM colloidal probe technique, scratch tests, and spectroscopic ellipsometry are employed to study the conformation of a poly(2-vinyl pyridine) brush grafted to a planar surface and its interaction with microsized silica spheres in solutions containing monovalent (Cl^?) and multivalent counterions (SO₄ ^2? and PO₄ ^3?) at pH 2.5. During approach of the sphere, steric repulsion is observed with all salts at any concentration. The approach force-distance curves are fitted according to the Alexander-de Gennes model in order to calculate the equilibrium brush thickness L. These data are compared to the brush thickness determined by ellipsometry and AFM scratch tests. Different values are obtained but all of them decrease with increasing salt concentration. This effect is enhanced by counterions of higher valence because they have a stronger screening effect and ion correlation due to their greater charge per unit volume. With NaCl solutions, a reswelling of diluted P2VP coils is observed at Cl^? concentrations >1 M. When the sphere is retracted, weak adhesion forces occur at Cl^? concentrations >1.3?×?10^?2 M and at all concentrations of SO₄ ^2? and PO₄ ^3?.     

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.     

Ce3Cl5[SiO4] und Ce3Cl6[PO4]: Ein chloridreiches Chloridsilicat und ‐phosphat des Cers im Vergleich

Ce₃Cl₅[SiO₄] and Ce₃Cl₆[PO₄]: A Chloride‐Rich Chloride Silicate of Cerium as Compared to the Phosphate By reacting CeCl₃ with CeO₂, cerium and SiO₂, or P₂O₅, respectively, in molar ratios of 5 : 3 : 1 : 3 or 8 : 3 : 1 : 2, respectively, in sealed evacuated silica tubes (7 d, 850 °C) colorless, rod‐shaped single crystals of Ce₃Cl₅[SiO₄] (orthorhombic, Pnma; a = 1619.7(2), b = 415.26(4), 1423.6(1) pm; Z = 4) and Ce₃Cl₆[PO₄] (hexagonal, P6₃/m; a = 1246.36(9), c = 406.93(4) pm; Z = 2) are obtained as products insensitive to air and water. Excess cerium trichloride as flux promotes crystal growth and can be rinsed off again with water after the reaction. The crystal structures are determined by discrete [SiO₄]^4– or [PO₄]^3– tetrahedra as isolated units. Both, the chloride silicate Ce₃Cl₅[SiO₄] and the chloride phosphate Ce₃Cl₆[PO₄], exhibit structural similarities to CeCl₃ (UCl₃ type), when four or three Cl^– anions are each substituted formally by one [SiO₄]^4– or [PO₄]^3– unit, respectively, in the tripled formula (Ce₃Cl₉). The coordination number for Ce³⁺ is thus raised from nine in CeCl₃ to ten in Ce₃Cl₅[SiO₄] and Ce₃Cl₆[PO₄], along with a drastic reduction of the molar volume with the transition from Ce₃Cl₉ (V_m = 186.17 cm³/mol) to Ce₃Cl₅[SiO₄] (V_m = 144.15 cm³/mol) and Ce₃Cl₆[PO₄] (V_m = 164.84 cm³/mol). The polyhedra of coordination around Ce³⁺ can be described as quadruple‐capped trigonal prisms, which in addition to seven Cl^– anions each also show another three oxygen atoms of two ortho‐silicate or ortho‐phosphate tetrahedra, respectively.     

Encapsulation of Halocarbons in a Tetrahedral Anion Cage

Caged supramolecular systems are promising hosts for guest inclusion, separation, and stabilization. Well‐studied examples are mainly metal‐coordination‐based or covalent architectures. An anion‐coordination‐based cage that is capable of encapsulating halocarbon guests is reported for the first time. This A₄L₄‐type (A=anion) tetrahedral cage, [(PO₄)₄ L ₄]^12?, assembled from a C₃‐symmetric tris(bisurea) ligand ( L ) and phosphate ion (PO₄^3?), readily accommodates a series of quasi‐tetrahedral halocarbons, such as the Freon components CFCl₃, CF₂Cl₂, CHFCl₂, and C(CH₃)F₃, and chlorocarbons CH₂Cl₂, CHCl₃, CCl₄, C(CH₃)Cl₃, C(CH₃)₂Cl₂, and C(CH₃)₃Cl. The guest encapsulation in the solid state is confirmed by crystal structures, while the host–guest interactions in solution were demonstrated by NMR techniques.     

A SIMPLE ROUTE FOR SYNTHESES OF TRIHALIDE-BRIDGED CARBONYL DIRUTHENIUM(II,III) COMPLEXES: CRYSTAL AND MOLECULAR STRUCTURE OF ttt-[RuIICl2(CO)2(PPh3)2],[(CO)(AsPh3)2RuII(μ-Cl3)RuIIICl2(AsPh3)] AND ([CO)(PPh3)2RuII(μ-Br3)RuIIIBr2(PPh3)], SPECTROSCOPIES,ELECTROCHEMISTRY AND PROPERTIES

Abstract

The triply halide-bridged binuclear complexes [Ru₂Cl₅(CO)(AsPh₃)₃] (AsPh₃ = triphenylarsine), [Ru₂Cl₅(CO)(PPh₃)₂(AsPh₃)] (PPh₃ = triphenylphosphine), [Ru₂Cl₅(CO)(AsPh₃)₂(PPh₃)], [Ru₂ Br₅(CO)(PPh₃)₃], [Ru₂Cl₅(CO)(P{p-tol}₃)₂(PPh₃)] (P{p-tol}₃ = tri-p-tolylphosphine) and [Ru₂ Br₂Cl₃(PPh₃)₂(AsPh₃)] were prepared from the precursor compounds ttt-[RuX₂(CO)₂(P)₂] (X = Cl or Br) and [RuY₃(P')₂S]·S (Y = Cl or Br; P=PPh₃, AsPh₃ or P{p- tol}₃ and P' = AsPh₃ or PPh₃; S=DMA or MeOH, where DMA = N,N'-dimethylacetamide). The molecular structures of the binuclear complexes [Ru₂Cl₅(CO)(AsPh₃)₃] (P2_1/c), [Ru₂Br₅(CO)(PPh₃)₃] (P2_1/c) and ttt-[RuCl₂(CO)₂(PPh₃)₂] (P1) were determined by X-ray diffraction methods. The complexes are always formed by two Ru atoms bridged through three halide anions, two of which are × type (from the Ru^II precursor) and the other is Y type (from the ruthenium^III precursor) confirming our previously suggested mechanism for obtaining this class of complexes. The Ru^II atom is also coordinated to a carbon monoxide molecule and two P ligands from the ttt-starting isomer whereas the Ru^III atom is bonded to two non-bridging Y halides and one P' molecule. The presence of Ru^III was confirmed by EPR data, a technique that was also useful to suggest the symmetry of the complexes. The absence of intervalence charge-transfer transitions (IT) in the near infrared spectrum confirms that the binuclear complexes have localized valence. The IR spectra of the complexes show; (CO) bands close to 1970 cm^?1 and ν(Ru-Cl) or(Ru-Br) bands at about 230–380 cm^?1 corresponding to halides at terminal or bridged positions. Two widely separated redox processes, Ru^II/Ru^II←Ru^II/Ru^III→Ru^III/Ru^III, were observed by cyclic voltammetry and differential pulse voltammetry.     

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.     

Pseudohalogeno‐Metallverbindungen. LXXVI Molekülstruktur von Tetrafulminatomercurat(II), [Hg(CNO)4]2–

Pseudohalogeno Metal Compounds. LXXVI Molecular Structure of Tetrafulminatomercurate, [Hg(CNO)₄]^2– Crystals of [AsPh₄]₂[Hg(CNO)₄] contain [AsPh₄]⁺ cations and [Hg(CNO)₄]^2– anions. The tetrafulminatomercurate ion forms a slightly distorted tetrahedron with linear fulminate ligands. In the crystal the [Hg(CNO)₄]^2– anions are separated by the AsPh₄⁺ cations which explains the thermal stability of this compound.