RuS4Cl12 und Ru2S6Cl16, zwei neue Ruthenium(II)‐Komplexe mit SCl2‐Liganden

RuS₄Cl₁₂ and Ru₂S₆Cl₁₆, Two New Ruthenium(II) Complexes with SCl₂ Ligands Ru powder was reacted with SCl₂ in closed silika ampoules at 140 °C. From the black solution three compounds RuS₄Cl₁₂ 1 , Ru₂S₆Cl₁₆ 2 , and Ru₂S₄Cl₁₃ 3 could be crystallized and characterized by x ray analysis. Black crystals of 1 (monoclinic, a = 9.853(1) Å, b = 11.63(1) Å, c = 15.495(1) Å, β = 105.23(1)°, space group P2₁/c, z = 4) are identified as Trichlorsulfonium‐tris(dichlorsulfan)trichloro‐ruthenat(II) SCl₃[RuCl₃(SCl₂)₃]. In the structure the complex anions fac‐[RuCl₃(SCl₂)₃]^– and the cations [SCl₃]⁺ are connected to ion pairs by three chlorine bridges. The brown crystals of 2 (triclinic, a = 7.754(2) Å, b = 7.997(2) Å, c = 10.708(2) Å, α = 103.74(3)°, β = 98.44(3)°, γ = 108.58(3)°, space group P‐1, z = 1) contain the binuclear complex Bis‐μ‐chloro‐dichloro‐hexakis(dichlorsulfan)‐diruthenium(II), (SCl₂)₃ClRu(μ‐Cl)₂RuCl(SCl₂)₃ with two fac‐RuCl₃(SCl₂)₃‐units connected by two chlorine bridges. 3 was identifyed as a known mixed valence Ru(II,III) binuclear complex [Cl₂(SCl₂)Ru(μ‐Cl)₃Ru(SCl₂)₃]. The vibrational spectra and the thermal behaviour of the compounds are discussed.     

Comparisons of energy disposal by the reactions of H atoms with Cl2, SCl2, S2Cl2 and SO2Cl2 from observation of HC1 infrared chemiluminescence

Arrested relaxation infrared chemiluminescence studies of the H + Cl₂, SCl₂, S₂Cl₂, SOCl₂ and SO₂-Cl₂ reactions have been made. The mean fraction of vibrational (stational) energy released to HCl is 0.40 (0.10); 0.40 (0.13); 0.38 (? 0.02); 0.33 (?0.02) and 0.36 (?0.02) for the series. Only the H + SCl₂ reaction shows a two component initial rotational distribution. The larger (f_V) and (f_R) from H + SCl₂, relative to the other polyatomic reagents, is consistent with the observation that this is the only reaction that shows forward scattering. The room temperature rate constants also were measured, relative to H + Cl₂, and were found to decline in the series from 0.68 for SCl₂ to 0.02 for SO₂Cl₂. All of these data support the suggestion (first made by Heydtmann and Polanyi) that the unusual rotational energy disposal pattern from H + SCl₂ is a consequence of migration of H from the initially encountered C1 to the second C1, which then forms the HCI product; this pathway augments the direct reactive pathway, which gives HCI in lower J states.     

Reactive scattering of hydrogen and deuterium atoms. III. Angular distributions for ClNO,SCl2, S2Cl2, SOCl2 and ClF3

Angular distributions for reactive scattering of hydrogen and deuterium atoms from five polyatomic molecules have been measured. With the exception of DCl from D + SCl₂ all angular distributions have a backward or sideways maximum.A measurement of the phase of the reactive signal shows that only 20% to 40% of the available energy goes into translation. Good agreement is found with a low pressure chemiluminescence experiment for H + SCl₂, while some differences are found for the higher pressure studies of H + S₂Cl₂ and H +SOCl₂. From the D + ClF₃ study some comments can be made on the reaction paths of the H₂ClF₃ chemical laser.     

Thiochloroarsenate(III): Darstellung,Schwingungsspektren und Kristallstrukturen von PPh4[As2SCl5] und (PPh4)2[As2SCl6] · C2H4Cl2

Thiochloroarsenates (III): Preparation, Vibrational Spectra, and Crystal Structures of PPh₄[As₂SCl₅] and (PPh₄)₂[As₂SCl₆] · C₂H₄Cl₂ PPh₄[As₂SCl₅] can be obtained from As₂S₃ + PPh₄Cl with HCl in CH₂Cl₂ or 1,2-C₂H₄Cl₂. It reacts with a second mole of PPh₄Cl to yield (PPh₄)₂[As₂SCl₆]. The latter also is formed by the reaction of As₂S₅ + 2 PPh₄Cl with HCl, a second product being (PPh₄)₂[As₂Cl₈]. The i.r. and Raman spectra of the title compounds are reported. Their crystal structures were determined by X-ray diffraction. Crystal data: PPh₄[As₂SCl₅], monoclinic, space group P2₁/n, a = 1175.8, b = 1508.0, c = 1593.4 pm, β = 96.22°, Z = 4; (PPh₄)₂[As₂SCl₆] · C₂H₄Cl₂, triclinic, P1, a = 1166.3, b = 1188.2, c = 2044.6 pm, α = 95.47, β = 97.53, γ = 111.05°, Z = 2. Including the lone electron pairs, the coordination of the As atoms in the [As₂SCl₅]^? ion is distorted trigonal-bipyramidal with the S, one Cl atom, and an electron pair in equatorial positions; the two bipyramids around the two As atoms share a common edge. The As atoms in the [As₂SCl₆]^2? ion have a distorted octahedral coordination, the two octahedra share a common face; the lone electron pairs are in the trans positions to the S atom.     

Über Addukte und Salze von Schwefelchloriden mit AlCl3

Adducts and Salts Formed by Sulphurchlorides with AlCl₃ The instability of the adduct 2 S₂Cl₂ · AlCl₃ is proven. S₂Cl₂ · AlCl₃ and S₂Cl₂ · 2 AlCl₃ reported in the literature could not be found under proper conditions, their formation seems improbable. The product 2 SCl₄ · 3 AlCl₃, obtained by the reaction of [SCl₃]⁺[AlCl₄]^? with elementary sulphur, is characterized as a double salt [SCl₃]₂+[AlCl₄]^? [Al₂Cl₇]^?. The [Al₂Cl₇]^? anion is also found as an intermediate during the thermal decomposition of [SCl₃]⁺[AlCl₄]^? and when metallic aluminium reacts directly with S₂Cl₂. For SCl₂ · AlCl₃, the ionic character with a chlorsulfenium cation [SCl]⁺ is proven spectroscopically.     

X@(HAlNH)12和X(HAlNH)12 (X＝F－, Cl－, Br－, O2－, S2－, Se2－)复合物的结构和稳定性

用DFT的B3LYP方法在6-31G(d)基组的水平上, 对闭式多面体簇合物(HAlNH)₁₂及其内含式X@(HAlNH)₁₂和外接式X(HAlNH)₁₂ (X＝F^－, Cl^－, Br^－, O^2－, S^2－, Se^2－)复合物的结构进行了构型优化和能量计算, 并讨论了几何构型、自然键轨道(NBO)、振动频率、能量参数及NMR数据与结构的关系, 最后得到复合物结构的稳定性信息, 具有T_h对称性的X@(HAlNH)₁₂ (X＝F^－, Cl^－, Br^－, S^2－, Se^2－)复合物和具有C₃对称性的O^2－@(HAlNH)₁₂复合物为内含式的基态结构, 从能量角度分析, 内含式复合物比外接式复合物的结构稳定.     

Synthese und Kristallstrukturen der Thiochloroantimonate(III) PPh4[Sb2SCl5] und (PPh4)2[Sb2SCl6] · CH3CN

Syntheses and Crystal Structures of the Thiochloroantimonates(III) PPh₄[Sb₂SCl₅] and (PPh₄)₂[Sb₂SCl₆]. CH₃CN (PPh₄)₂Sb₃Cl₁₁, obtained from Sb₂S₃, PPh₄Cl and HCl, reacts with Na₂S₄ in acetonitrile forming PPh₄[Sb₂SCl₅]. From this and Na₂S₄ or from (PPh₄)₂[Sb₂Cl₈] and Na₂S₄ or K₂S₅ in acetonitrile (PPh₄)₂[Sb₂SCl₆] · CH₃CN is obtained. Data obtained from the X-ray crystal structure determinations are: PPh₄[Sb₂SCl₅], monoclinic, space group P2₁/c, a = 1002.9(3), b = 1705.6(5), c = 1653.7(5) pm, β = 99.12(2)°, Z = 4, R = 0.068 for 1283 reflextions; (PPh₄)₂[Sb₂SCl₆] · CH₃CN, triclinic, space group P1 , a = 1287.8(7), b = 1343.6(9), c = 1696.5(9) pm, α = 69.82(5), β = 85.08(4), γ = 71.54(6)°, Z = 2, R = 0.059 for 6409 reflexions. In every anion two Sb atoms are linked via one sulfur and one ore two chloro atoms, respectively. Paris of [SbSCl₅]^? ions are associated via Sb …? S and Sb …? Cl contacts forming dimer units. In both compounds every Sb atom has a distorted octahedral coordination when the lone electron pair is included in the counting.     

Electronic structure and one-electron properties of the MoO2Cl2 molecule. Electronic spectra of the MoO2Cl2, MoO2Br2 and WO2Br2 molecules

The SCF-X -SW method in an overlapping atomic spheres approximation has been used to calculate the electronic structure, ionization potentials, energies and oscillator strengths of the allowed optical transitions and also some of the one-electron properties of the MoO₂Cl₂ molecule. The electronic absorption spectra of vapours over molybdenum and tungsten dioxodibromides have been measured. Interpretation of the experimental electronic absorption spectra of the MoO₂Cl₂, MoO₂Br₂ and WO₂Br₂ molecules is discussed.     

Single-crystal structure of Cs2Re6S6Br8 rhenium thiobromide with acentric Re6 octahedral cluster units

Cs₂Re₆S₆Br₈ (trigonal, a = 10.001(5) Å, c = 14.676(5) Å) exhibits the same structure as Cs₂Mo₆Cl₈Br₆ and Cs₂Mo₆Br₁₄ that were described in a noncentro-and centrosymmetric space groups, respectively. The structure has been refined in P31c space group from a single crystal of actual composition Cs_1.95(1)Re₆S_5.82(3)Br_8.19(3) close to the cesium-rich end of the solid solution Cs₂Re₆S₆Br₈ — CsRe₆S₅Br₉. The centrosymmetry is respected by almost all the atoms of the asymmetric unit, but it is clearly broken by significant differences in the S/Br statistical distribution of the disordered “inner” ligands around the Re₆ cluster. Structural refinements from data collected at 100 K revealed that the Cs cation disorder is static. From the structure refinements, the stable isomers of the [Re₆S₆Br₂] and [Re₆S₅Br₃] cluster cores have been unambiguously determined.     

Investigation on the mechanism and applications of the reaction Cl2+2HBr=2HCl+Br2

The mechanism of reaction Cl₂+2HBr=2HCl+Br₂ has been carefully investigated with density functional theory (DFT) at B3LYP/6-311G^** level. A series of three-centred and four-centred transition states have been obtained. The activation energy (138.96 and 147.24 kJ/mol, respectively) of two bimolecular elementary reactions Cl₂+HBr→HCl+BrCl and BrCl+HBr→HCl+Br₂ is smaller than the dissociation energy of Cl₂, HBr and BrCl, indicating that it is favorable for the title reaction occurring in the bimolecular form. The reaction has been applied to the chemical engineering process of recycling Br₂ from HBr. Gaseous Cl₂ directly reacts with HBr gas, which produces gaseous mixtures containing Br₂, and liquid Br₂ and HCl are obtained by cooling the mixtures and further separated by absorption with CCl₄. The recovery percentage of Br₂ is more than 96%, and the Cl₂ remaining in liquid Br₂ is less than 3.0%. The paper provides a good example of solving the difficult problem in chemical engineering with basic theory.     

Die Kristallstrukturen von Pb4SeBr6, Pb5S2J6 und Pb7S2Br10

Crystal Structures of Pb₄SeBr₆, Pb₅S₂I₆, and Pb₇S₂Br₁₀. The crystal structures of Pb₄SeBr₆, Pb₅S₂I₆ and Pb₇S₂Br₁₀ have been determined from single crystal X-ray analyses. Unit cell data see “Inhaltsübersicht”. The compounds have common structural features with the pure halides of lead. In Pb₄SeBr₆ all Pb atoms have trigonal prismatic coordination by Br(Se), additional neighbours above the prism faces completing the coordination number to 7, 8 or 9. In Pb₅S₂I₆ some of the Pb atoms are surrounded by 6 I + 1 S or 5 I + 3 S in the same extended trigonal prismatic arrangement, others are in the centers of PbI₆ octahedra. Pb₇S₂Br₁₀ is isostructural with Th₇S₁₂ with statistical occupancy of part of the metal and nonmetal positions.     

Beiträge zur Chemie der Oxidhalogenide von Molybdän und Wolfram. I. Sättigungsdruck und Bildungsenthalpie von MoO2Br2 und MoO2CI2

Molybdenum dioxiddibromide and -dichloride have been prepared from MoO₂, Br₂, und Cl₂, respectively, and their chemical and thermochemival behaviour was studied. Their enthalpies of formation, ΔH°, have been determined from the solution enthalpies of MoO₂Br₂, and MOo₂Cl₂, in aqueous NaOH (data see ?Inhaltsübersicht”?). From their sublimation pressures, p, the enthalpies, ΔH° (subl.), and entropies, ΔS° (subl.), of sublimation have been evaluated (data see above).     

Investigation on the mechanism and applications of the reaction Cl2+2HBr=2HCl+Br2

The mechanism of reaction Cl₂+2HBr=2HCl+Br₂ has been carefully investigated with density functional theory (DFT) at B3LYP/6-311G^** level. A series of three-centred and four-centred transition states have been obtained. The activation energy (138.96 and 147.24 kJ/mol, respectively) of two bimolecular elementary reactions Cl₂+HBr→HCl+BrCl and BrCl+HBr→HCl+Br₂ is smaller than the dissociation energy of Cl₂, HBr and BrCl, indicating that it is favorable for the title reaction occurring in the bimolecular form. The reaction has been applied to the chemical engineering process of recycling Br₂ from HBr. Gaseous Cl₂ directly reacts with HBr gas, which produces gaseous mixtures containing Br₂, and liquid Br₂ and HCl are obtained by cooling the mixtures and further separated by absorption with CCl₄. The recovery percentage of Br₂ is more than 96%, and the Cl₂ remaining in liquid Br₂ is less than 3.0%. The paper provides a good example of solving the difficult problem in chemical engineering with basic theory.     

Crystallochemistry of mercury chalcogenides. IV. Crystalline structure of two polymorphous modifications of the mercury sulfochalcogenide Hg3S2Br1.5Cl0.5

Two modifications of a new mercury sulfohalide of Hg₃S₂Br_2−x Cl_x (x = 0.5) composition have been grown from the gas phase and explored by X-ray structural analysis. The compounds were obtained at an attempt to synthesize an analogue of the rare mineral arzakite Hg₃S₂(Br, Cl)₂ (Br > Cl). The refinement of the crystalline structures of monoclinic (I) and cubic (II) phases (I: a = 17.824(4) Å, b = 9.238(2) Å, c = 10.269(2) Å, β = 115.69(1)°, V = 1523.8(5) ų, space group C2/m, Z = 8, R = 0.0513; II: a = 18.248(2) Å, V = 6076.4(12) ų, space group Pm3ˉn, Z = 32, R = 0.038) has shown that they are polymorphous modifications of the compound of Hg₃S₂Br_1.5Cl_0.5 formula. The monoclinic modification I is isostractural to the synthetic compound α-Hg₃S₂Br₂. Modification II is isostructural to synthetic β-Hg₃S₂Cl₂. In both structures, each atom S has in its surrounding three atoms of Hg forming umbrella-type groups SHg₃ with spaces Hg—S 2.366–2.430 Å and angles HgSHg 95.66–97.60°. SHg₃-fragments are bound by Hg-apices with the formation of isolated cubic groups [Hg₁₂S₈]. Like that in other structures of mercury chalcohalides, the main role in structure-forming of the investigated compounds is played by atoms of halogens creating a cubic sublattice in which radicals Hg—S are arranged. Original Russian Text Copyright ? 2006 by N. V. Pervukhina, S. A. Magarill, D. Yu. Naumov, S. V. Borisov, V. I. Vasil’yev, and B. G. Nenashev __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 47, No. 2, pp. 318–323, March–April, 2006.     

Synthese und Struktur des μ-Sulfido-μ-disulfido-octabromodiwolframat(V)-Ions [W2S3Br8]2−

Synthesis and Structure of μ-Sulfido-μ-disulfido-octabromoditungstate(V), [W₂S₃Br₈]^?2 Tungsten hexabromide reacts with H₂S in dichloromethane yielding a brown product which, by addition of tetraphenylphosphonium bromide in CH₂Cl₂, is converted to brown, crystalline (PPh₄)₂[Br₄W(μ-S)(μ-S₂)WBr₄] · CH₂Cl₂ · CH₂S. Its IR spectrum is reported, its crystal structure was determined by X-ray diffraction (2330 reflexions, R = 0.097). Crystal data: orthorhombic, Pnma, a = 1 766.5, b = 2 412.7, c = 1 416.3 pm, Z = 4. In the diamagnetic [W₂S₃Br₈]^2? ions the two W atoms are linked via a sulfido and a disulfido bridge and by a W? W bond.     

Die Kristallstruktur von SCl3[Re2Cl9] und ihre Verwandtschaft zum RuBr3‐Typ

The Crystal Structure of SCl₃[Re₂Cl₉] and its Relation to the RuBr₃ Type SCl₃[Re₂Cl₉] was obtained from the reaction of rhenium and SCl₂ at 400 °C. The X‐ray crystal structure determination revealed a monoclinic structure, a = 834.1 pm, b = 1053.3 pm, c = 866.1 pm, β = 91.90°, space group P2₁/m, R₁ = 0.058. The SCl₃⁺ and Re₂Cl₉^– ions have the known structures; the ReRe bond length in the face‐sharing bioctahedron is 272.2 pm. The crystal packing can be derived from the RuBr₃ structure type, which has infinite columns of face‐sharing octahedra; one quarter of the metal atoms are removed and another quarter are replaced by sulfur atoms. The chlorine atoms form a slightly distorted hexagonal closest‐packing. The symmetry relationships are shown in a family tree of group–subgroup relations.     

Massenspektrometrische und gravimetrische KNUDSEN-Effusionsmessungen an Wolframdioxid-dibromid WO2Br2

Mass-spectrometric and Gravimetric KNUDSEN Effusion Measurements on Tungsten Dioxidedibromide, WO₂Br₂ The sublimation enthalpy ΔH⁰ (subl., WO₂Br₂, 298) of WO₂Br₂ has been determined by means of the abovementioned methods and using an approximate ΔCp (subl.) value. Furthermore, the sublimation entropy, ΔS⁰(subl., WO₂Br₂, 298); the enthalpy of formation of gaseous WO₂Br₂, ΔH (WO₂Br₂, g, 298); and the entropy of gaseous WO₂Br₂, S⁰(WO₂Br₂, g, 298), have been evaluated. Obtained data: see ?Inhaltsübersicht”?.     

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.     

Die Reaktion von UV- und UVI-Verbindungen mit SOCl2

Reaction of U^V and U^VI Compounds with SOCl₂ UO₃, UO₂Cl₂, UCl₆, and UCl₅ reacted with OSCl₂ yield always UCl₅ · SCl₂, [SCl₃]⁺ [UCl₆]^? or a mixture of these compounds, but not an adduct UCl₅ · OSCl₂. An X-ray study was carried out with single crystals of [SCl₃]⁺[UCl₆]^?. It crystallizes in the orthorhombic space group P2₁2₁2₁ with the lattice constants a = 1066.8, b = 1071.2, c = 1133.3 pm and with Z = 4, containing isolated pyramidal SCl₃⁺ (r_SCl = 196.2 ± 1.1 pm ?SCl₂ = 102.34 ± 1.13°) and octahedral UCl₆^? ions (r_UCl = 251.1 ± 2.6 pm).     

Structural chemistry of mercury chalcohalides. III. Crystal structure of Hg<Subscript>3</Subscript>S<Subscript>2</Subscript>Cl<Subscript>1.5</Subscript>Br<Subscript>0.5</Subscript> polymorphs

Single crystals of two new mercury thiohalides of the composition Hg₃S₂Cl_{2? x}Br_x(x = 0.5) have been grown from gas phase and studied by X-ray crystallography. Structure refinement for monoclinic (I) and cubic (II) phases (I: a = 16.841(2) Å, b = 9.128(2) Å, c = 9.435(4) Å; β = 90.080(10)°, V = 1450.3(7) ų, space group _C2/_{m, Z} = 8, _R = 0.0528; II: a = 18.006(2) Å, V = 5837.8(11) ų, space group \(Pm\bar 3n\), Z = 32, R = 0.0503) clearly shows that they are polymorphs of the same composition Hg₃S₂Cl_1.5Br_0.5. The monoclinic modification I is similar to the synthetic phases γ-Hg₃S₂Cl₂, β-Hg₃S₂Br₂, Hg₃Se₂Br₂ and to the analogue of radtkeite mineral, Hg₃S₂ClI. The modification II is isostructural to the synthetic β-Hg₃S₂Cl₂. In both structures, each S atom coordinates three Hg atoms with the formation of pyramidal SHg₃ units (Hg-S 2.37–2.48 Å; HgSHg 93.1–97.5 ). The SHg₃ units are linked through Hg vertices into corrugated layers [Hg₁₂S₈]_∞∞ (I) and isolated cubic groups [Hg₁₂S₈] (II). Similarly to other mercury chalcohalides, the crystal structures are basically determined by the halogen atoms which form a cubic sublattice incorporating the Hg-S moieties.