Periphere Anbindung von Quecksilber(II)-iodid an dreikernige Molybdän-Schwefel-Dithiophosphinatocluster: [Mo3S4(R2PS2)4HgI2] (R = Et,Pr)

Peripheral Bonding of Mercury(II) Iodide to Trinuclear Molybdenum-Sulfur-Dithiophosphinato Clusters: [Mo₃S₄(R₂PS₂)₄HgI₂] (R = Et, Pr) Reaction of Mo₃S₄(R₂PS₂)₄ 1 (a : R = Et, b : R = Pr) with HgI₂ in THF yields the diamagnetic title complexes [Mo₃S₄(R₂PS₂)₄HgI₂] 3 . The crystal structure of [ 3a (H₂O)] · 2 CH₂Cl₂ shows the complexes to consist of a triangular array of Mo atoms which are bridged by μ₂? S atoms and capped by a μ₃? S atom. Each of the Mo atoms is chelated by a dithiophosphinato ligand Et₂PS₂^? and in addition two Mo atoms are bridged by a Et₂PS₂^? ligand while the H₂O molecule is bonded weakly to the third Mo atom. Thus, all Mo atoms reveal a distorted octahedral coordination sphere. HgI₂ is ?peripherally”? bonded to the cluster via two S atoms, one of which belongs to a chelating ligand and the other one to the bridging ligand. Space group P1 , lattice constants a = 12.157(2), b = 15.284(3), c = 16.049(3) Å, α = 115.56(1), β = 107.35(1), and γ = 94.62(1)°; Z = 2, d_calc = 2.23 mg/mm³; 4 236 observed reflections, R = 0.068. In organic solvents complexes 3 are strong electrolytes. VT-³¹P NMR data suggest a stepwise dissociation of 3 with formation of [Mo₃S₄(R₂PS₂)₃] ⁺[(R₂PS₂)HgI₂]^? and elimination of the bridging ligand from the cluster.     

Three New Thioantimonates(V): Solvothermal Syntheses and Crystal Structures of [M(chxn)3]3(SbS4)2·4H2O (M = Ni,Co) and [Co(dien)2][Co(tren)SbS4]2·4H2O

The three new thioantimonates(V) [Ni(chxn)₃]₃(SbS₄)₂·4H₂O ( I ), [Co(chxn)₃]₃(SbS₄)₂·4H₂O ( II ) (chxn is trans‐1,2‐diaminocyclohexane) and [Co(dien)₂][Co(tren)SbS₄]₂·4H₂O ( III ) (dien is diethylenetriamine and tren is tris(2‐aminoethyl)amine) were synthesized under solvothermal conditions. Compounds I and II are isostructural crystallizing in space group C2/c. The structures are composed of isolated [M(chxn)₃]²⁺ complexes (M = Ni, Co), [SbS₄]^3? anions and crystal water molecules. Short S···N/S···O/O···O separations indicate hydrogen bonding interactions between the different constituents. Compound III crystallizes in space group and is composed of [Co(dien)₂]²⁺ and [Co(tren)SbS₄]^? anions and crystal water molecules. In the cationic complex the Co²⁺ ion is in an octahedral environment of two dien ligands whereas in [Co(tren)SbS₄]^? the Co²⁺ ion is in a trigonal bipyramidal coordination of four N atoms of tren and one S atom of the [SbS₄]^3? anion, i.e., two different coordination polyhedra around Co²⁺ coexist in this compound. Like in the former compounds an extended hydrogen bonding network connects the complexes and the water molecules into a three‐dimensional network.     

Die Kristallstruktur von (PPh4)2[Mo2(O2C?Ph)4Br2] · 2 CH2Br2

Crystal Structure of (PPh₄)₂[Mo₂(O₂C? Ph)₄Br₂] · 2 CH₂Br₂ The title compound, prepared by the reaction of Mo₂(O₂C? Ph)₄ with PPh₄Br and PPh₄N₃, respectively, under the assistance of CH₂Br₂, was characterized by an X-ray structure determination. Space group P2₁/n, Z = 2, R = 0.074 (5261 independent observed reflexions). The lattice dimensions are at ?70°C: a = 1562.9, b = 1406.2, c = 1662.1 pm, β = 94.11°. the compound consists of PPh₄^⊕ ions, CH₂Br₂ molecules, and centrosymmetric anions [Mo₂(O₂C? Ph)₄Br₂]^2?. The axis Br? Mo?Mo–Br is nearly linear (bond angle 175.6°) with bond lengths MoMo = 212.3 pm and Mo? Br = 303 pm, corresponding with a weak electrostatic Mo? Br bond. In the FIR spectrum the Mobr stretching vibration is found at 85 cm^?1, which corresponds with the low value of the force constant of 0.24 N · cm^?1.     

Elektronenstruktur von strukturell offenen Derivaten des [Mo6X14]2−-Clusters: [Mo5Cl13]2− und [Mo4I11]2−

Electronic Structure of Structural Open Derivatives of the [Mo₆X₁₄]^2?-Cluster: [Mo₅Cl₁₃]^2? and [Mo₄I₁₁]^2? The electronic structure of structural open derivatives of the [Mo₆X₁₄]^2?-cluster [Mo₅Cl₁₃]^2? and [Mo₄I₁₁]^2? has been studied by the EHMO method. In [Mo₅Cl₁₃]^2? 9 occupied MO's with dominant Mo4d character are responsible for the formation of the 8 metal-metal bonds. In [Mo₄I₁₁]^2? the stronger covalent character of the Mo? I bonds affects the localization and the energy of molecular orbitals and also the charge distribution. The metal-metal bonds are formed by 8 MO's containing considerable participation of halogen AO's contrary to the chloride cluster. There is no bonding between the Mo atoms at the wing tips of the Mo₄ butterfly and the reason for decreasing the dihedral angle between the Mo₃ planes in [Mo₄I₁₁]^2? compared with the octahedral angle is apparently the stabilization of the whole system (Mo? Mo and Mo? I bonds). The unpaired electron occupies in both clusters a slightly antibonding (with regard to the Mo? Mo bonds) orbital.     

Einige Reaktionen mit [Mo6Cl8]Cl4

Some Reactions with [Mo₆Cl₈]Cl₄ The reaction of [Mo₆Cl₈]Cl₄ with different chemical agents has been investigated: The methoxylation depends on the CH₃O^? concentration in CH₃OH. The reaction with HF leads to a partial fluorinated [Mo₆Cl₈] product. With NH₄F (NH₄)₂[Mo₆Cl₈]F₆ in formed, the hydrolysis of which leads to [Mo₆Cl₈]F₃(OH) · 2.5 H₂O. This compound can be decomposed thermically into [Mo₆Cl₈]O₂. [Mo₆Br₈]F₆^2? on hydrolysis leads to [Mo₆Br₈]F₃(OH) · 5 H₂O. With CsF Cs₂[Mo₆Cl₈]F₆ is formed, which by hydrolysis is transformed into [Mo₆Cl₈]F₃(OH) · 2.5 H₂O and possibly to [Mo₆Cl₈]F₄ · xH₂O(?). In reaction of [Mo₆Cl₈]Cl₄ with H₂SO₄ one gets [Mo₆Cl₈](SO₄)₂. Salts e. g. [(C₆H₅)₄As]₂[Mo₆Cl₈](OC₆F₅)₆ and adducts e. g. [Mo₆Cl₈](OC₆F₅)₄ · 2 HMPA are prepared. The compounds have been characterized by X-ray powder-diagramms and by IR-spectra.     

Co(en)3[B4O5(OH)4]Cl·3H2O和[Ni(en)3][B5O6(OH)4]2·2H2O的合成、结构以及热力学性质

利用水热法合成了两种过渡金属配合物为模板剂的含水硼酸盐晶体Co(en)3[B4O5(OH)4]Cl·3H2O(1) 和 [Ni(en)3][B5O6(OH)4]2·2H2O (2),并通过元素分析、X射线单晶衍射、红外光谱及热重分析对其进行了表征。化合物1晶体结构的主要特点是在所有组成Co(en)33+, [B4O5(OH)4]2–, Cl– 和 H2O之间通过O–H…O、O–H…Cl、N–H…Cl和N–H…O四种氢键连接形成网状超分子结构。化合物2晶体结构的特点是[B5O6(OH)4]–阴离子通过O–H…O氢键连接形成沿a方向有较大通道的三维超分子骨架,模板剂[Ni(en)3]2+阳离子和结晶水分子填充在通道中。     

Synthesis and crystal structure of tetraethylammonium-μ-trichloro-heptachloro-diaqua-trirhenate(III)-dihydrate,NEt4[Re3Cl10(H2O)2] · 2 H2O

NEt₄[Re₃Cl₁₀(H₂O)₂] · 2 H₂O ( 1 ) was obtained from hydrochloric acid solutions of ReCl₃ and tetraethylammonium chloride, NEt₄Cl, by isothermal evaporation as dark red crystals. 1 crystallizes in the orthorhombic crystal system, space group Pnma, Z = 4, with a = 1838,7(2), b = 1456.9(1), c = 972.08(7) pm, V_m = 391.81(6) cm³ · mol^?l. The crystal structure consists of [Re₃Cl₁₀(H₂O)₂]^? anions that are arranged in the fashion of a hexagonal closest-packing of spheres. These are held together by partially disordered NEt₄⁺ cations and are bound into a hydrogen bonding system with the crystal water.     

Chloro- und Polyselenoselenate(II) Darstellung,Struktur und Eigenschaften von [Ph3(C2H4OH)P]2[SeCl4] · MeCN, [Ph4P]2[Se2Cl6] und [Ph4P]2[Se(Se5)2]

Chloro- and Polyselenoselenates(II): Synthesis, Structure, and Properties of [Ph₃(C₂H₄OH)P]₂[SeCl₄] · MeCN, [Ph₄P]₂[Se₂Cl₆], and [Ph₄P]₂[Se(Se₅)₂] By symproportionation of elemental selenium and SeCl₄ in polar protic solvents the novel chloroselenates(+II), [SeCl₄]^2? and [Se₂Cl₆]^2?, could be stabilized; they were crystallized with voluminous organic cations. They were characterized from complete X-ray structure analysis. Yellow-orange [Ph₃(C₂H₄OH)P]₂[SeCl₄] · MeCN (space group P1 , a = 10.535(4), b = 12.204(5), c = 16.845(6) Å, α = 77.09(3)°, β = 76.40(3)°, γ = 82.75(3)° at 140 K) contains in its crystal structure monomeric [SeCl₄]^2? anions with square-planar coordination of Se(+II). The mean Se? Cl bond length is 2.441 Å. In yellow [Ph₄P]₂[Se₂Cl₆] (space group P1 , a = 10.269(3), b = 10.836(4), c = 10.872(3) Å, α = 80.26(3)°, β = 79.84(2)°, γ = 72.21(3)° at 140 K) a dinuclear centrosymmetric [Se₂Cl₆]^2? anion, also with square-planar coordinated Se(+II), is observed. The average terminal and bridging Se? Cl bond distances are 2.273 and 2.680 Å, respectively. From redox reactions of elemental Se with boranate/thiolate in ethanol/DMF the bis(pentaselenido)selenate(+II) anion [Se(Se₅)₂]^2? was prepared as a novel type of a mixed-valent chalcogenide. In dark-red-brown [Ph₄P]₂[Se(Se₅)₂] (space group P2₁/n, a = 12.748(4), b = 14.659(5), c = 14.036(5) Å, β = 108.53(3)° at 140 K) centrosymmetric molecular [Se(Se₅)₂]^2? anions with square-planar coordination of the central Se(+II) by two bidentate pentaselenide ligands is observed (mean Se? Se bond lengths: 2.658 Å at Se(+II), 2.322 Å in [Se₅]_2?). The resulting six-membered chelate rings with chair conformation are spirocyclically linked through the central Se(+II). The vibrational spectra of the new anions are reported.     

Thiochloroanionen von Molybdän(IV). Die Kristallstruktur von (NEt4)3[Mo3(μ3-S)(μ-S2)3Cl6]Cl · CH2Cl2 Kristallstruktur,EPR-Spektrum und magnetische Eigenschaften von (NEt4)2[Mo2(μ-S2)(μ-Cl)2Cl6]

Thiochloro Anions of Molybdenum (IV). Crystal Structure of (NEt₄)₃[Mo₃(μ₃-S)(μ-S₂)₃Cl₆]Cl μ CH₂Cl₂. Crystal Structure, Magnetic Properties, and EPR-Spectrum of (NEt₄)₂ [Mo₂(μ-S₂)(μ-Cl)₂Cl₆] From molybdenum pentachloride and tetraethylammonium hydrogensulfide in CH₂Cl₂ an insoluble product of composition (NEt₄)₂[Mo₂S₃Cl₉] was obtained along with a brown solution, from which (NEt₄)₂[Mo₂(S₂)Cl₈] was crystallized. The insoluble product and NEt₄Cl react in CH₂Cl₂ to yield, among others, (NEt₄)₃[Mo₃(S)(S₂)₃Cl₆]Cl · CH₂Cl₂. The latter crystallizes in the orthorhombic space group Pnma, a = 2495.8, b = 1501.2, c = 1295.6 pm, Z = 4. According to the crystal structure determination (3070 observed reflexions, R = 0.049) the [Mo₃(S)(S₂)₃Cl₆]^2? ion consists of an Mo₃ triangle with Mo? Mo bonds, each side of the triangle is bridged by disulfido groups and one sulfur atom is capped over the Mo₃ triangle; the single chloride ion is looseley associated to three S atoms. (NEt₄)₂[Mo₂(S₂)Cl₈] also crystallizes in the space group Pnma, a = 1425.6, b = 1129.9, c = 2004.7 pm, Z = 4; structure determination with 1703 observed reflexions, R = 0.061. In the [Mo₂(S₂)Cl₈]^2? ion the Mo atoms are bridged via one disulfido group and two chlorine atoms. There is a Mo? Mo bond, but according to the magnetic properties and the EPR spectrum each Mo atom still possesses one unpaired electron.     

Darstellung von trans-[Mo6Cl8]Cl4Br22−ausgehend von kristallisierten [Mo6Cl8]Cl4(H2O)2 und die Kristallstruktur von [(C6H5)4As]2[Mo6Cl8]Cl4Br2

Preparation of trans-[Mo₆Cl₈]Cl₄Br₂^2? Starting from Crystalline [Mo₆Cl₈]Cl₄(H₂O)₂ and Crystal Structure of [(C₆H₅)₄As]₂[Mo₆Cl₈]Cl₄Br₂ The synthesis of the title compound is successful if the crystallized [(Mo₆Cl₈)Cl₄(H₂O)₂] containing the H₂O molecules in trans-position reacts with HBr + [(C₆H₅)₄As]Br in ethanol in a heterogeneous reaction. The X-ray structure investigation confirms the existence of discrete trans-Br-substituted cluster anions of composition [(Mo₆Cl₈)Cl₄Br₂]^2? in the crystal. The reaction in homogeneous solutions proceeds to Br-enriched compounds. [(C₆H₅)₄As]₂[(Mo₆Cl₈)Cl₄Br₂] crystallizes in the triclinic space group P¯1 with a = 11.071(2), b = 11.418(2), c = 12.813(2) Å, α = 116.10(2), β = 95.27(2) and γ = 94.41(2)° (?133°C). The crystal structure at ?133°C was determined from single crystal X-ray diffraction data (R₁ = 0.026). The [(Mo₆Cl₈)Cl₄Br₂]^2?-anions are not completely ordered but distributed statistically among the three positions which are possible within the limits of the ordered [Mo₆Cl₈]-cores (ratio 11:5:4). The frameworks of the anions consist of Mo₆ cluster units with (slightly distorted) octahedral arrangement of the metal atoms (d(Mo? Mo): 2.600(1) up to 2.614(1) Å), which are coordinated by the halogeno ligands in a square-pyramidal manner. The details of the structure will be discussed and compared with similar [(Mo₆X₈)Y₄] cluster units (X, Y ? Cl, Br).     

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°.     

Über die Reaktion von 2,2-Dimethylpropylidinphosphan mit Molybdänpentachlorid; die Kristallstruktur von [Mo2Cl6(α,α′-Dipyridyl)3]

Reaction of 2,2-Dimethylpropylidynephosphine with Molybdenum Pentachloride; Crystal Structure of [Mo₂Cl₆(α,α′-dipyridyl)₃] 2,2-Dimethylpropylidynephosphine and molybdenum pentachloride dissolved in POCl₃ react with oxydation of the phosphorus and reduction of the molybdenum atom to give the alkyne complex [Mo₂Cl₄(μ-Cl)₂(μ-H₉C₄? C?C? C₄H₉)(OPCl₃)₂]. Addition of α,α′-dipyridyl or of methyltriphenylphosphonium chloride in dichloromethane results in a displacement of the ligands POCl₃ and H₉C₄? C?C? C₄H₉ from this complex and in the formation of [Mo₂Cl₆(dipy)₃] or [(H₅C₆? )₃P? CH₃]₃[Mo₂Cl₉]. Besides the latter compound small amounts of [(H₅C₆? )₃P? CH₃]₂[MoCl₆] can be isolated from the reaction mixture. [Mo₂Cl₆(dipy)₃] which has already been prepared by other methods crystallizes in the monoclinic space group P2₁/c with {a = 1612; b = 148; c = 1296 pm; γ 109.3°; Z = 4} at 20°C. As shown by a crystal structure determination the complex is built up from [MoCl₂(dipy)₂]⁺ cations and [MoCl₄(dipy)]^? anions. The molybdenum atoms are both octahedrally surrounded. With average values of 238 and 243 pm the Mo? Cl bond distances in the cation, where a cis-arrangement of the chlorine atoms is observed, and in the anion differ significantly from each other. [Mo₂Cl₆(dipy)₃] which has already been prepared by other methods crystallizes in the monoclinic space group P2₁/c with {a = 1612; b = 148; c = 1296 pm; γ = 109.3°; Z = 4} at 20°C. As shown by a crystal structure determination the complex is built up from [MoCl₂(dipy)₂]⁺ cations and [MoCl₄(dipy)]^? anions. The molybdenum atoms are both octahedrally surrounded. With average values of 238 and 243 pm the Mo? Cl bond distances in the cation, where a cis-arrangement of the chlorine atoms is observed, and in the anion differ significantly from each other.     

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.     

On the preparation of binuclear S,S bridged molybdenum(V) complexes crystal and molecular structure of [Mo2S4(Et2dtc)2]

MoO₄^2? is reduced by diethyldithiocarbamate (Et₂dtc^?) on prolonged digestion in aqueous medium whereby the complex [Mo₂^VO₂S₂(Et₂dtc)₂] is formed. The central moiety Mo₂O₂S₂²⁺ has a high formation tendency. When [Mo₂^V(S₂)₆]^2? is refluxed with Et₂dtc^? in ethanol, [Mo₂^VS (Et₂dtc)₂] is formed, the X-ray crystal structure of which has been determined (space group P2₁2₁2₁, a = 10.550(2) Å, b = 13.820(5) Å, c = 14.723(12) Å, d_c = 1.90 g · cm^3?, Z = 4). The Mo? Mo distance of the diamagnetic compound is 2.817(2) Å and the average Mo=S_t distance 2.099(4) Å.     

Synthese und Kristallstruktur von (PPh4)2[Mo2(S2)2Cl8] · 2 CH3CN und seine topotaktische Umwandlung zu (PPh4)2[Mo2(S2)2Cl8]

Synthesis and Crystal Structure of (PPh₄)₂[Mo₂(S₂)₂Cl₈] · 2 CH₃CN and its Topotactic Transformation to (PPh₄)₂[Mo₂(S₂)₂Cl₈] MoS₂Cl₃ was prepared from molybdenum and S₂Cl₂ at 200 °C. Its reaction with PPh₄Cl in acetonitrile yielded (PPh₄)₂[Mo₂(S₂)₂Cl₈] · 2 CH₃CN. In vacuum or upon warming, it loses the acetronitrile without degradation of the crystals. According to the X-ray crystal structure determinations both compounds, with and without acetonitrile, are triclinic. They contain the same [Cl₄Mo(μ-S₂)₂MoCl₄]^2– ions, in which the Mo atoms are joined by two disulfido groups and an Mo–Mo bond. Details of the crystal packings and their topotactic transformation are given.     

Chalkogenohalogenogallate(III) und -indate(III): Eine neue Verbindungsklasse in der dritten Hauptgruppe. Synthese und Struktur von [Ph4P]2[In2SX6], [Et4N]3[In3E3Cl6] · MeCN und [Et4N]3[Ga3S3Cl6] · THF (X = Cl,Br; E = S,Se)

Chalcogenohalogenogallates(III) and -indates(III): A New Class of Compounds for Elements of the Third Main Group. Preparation and Structure of [Ph₄P]₂[In₂SX₆], [Et₄N]₃[In₃E₃Cl₆] · MeCN and [Et₄N]₃[Ga₃S₃Cl₆] · THF (X = Cl, Br; E = S, Se) [In₂SCl₆]^2?, [In₂SBr₆]^2?, [In₃S₃Cl₆]^3?, [In₃Se₃Cl₆]^3?, and [Ga₃S₃Cl₆]^3? were synthesised as the first known chalcogenohalogeno anions of main group 3 elements. [Ph₄P]₂[In₂SCl₆] ( 1 ) (P1 ; a = 10.876(4) Å, b = 12.711(6) Å, c = 19.634(7) Å, α = 107.21(3)°, β = 96.80(3)°, γ = 109.78(3)°; Z = 2) and [Ph₄P]₂[In₂SBr₆] ( 2 ) (C2/c; a = 48.290(9) Å, b = 11.974(4) Å, c = 17.188(5) Å, β = 93.57(3)°, Z = 8) were prepared by reaction of InX₃, (CH₃)₃SiSSi(CH₃)₃ and Ph₄PX (X = Cl, Br) in acetonitrile. The reaction of MCl₃ (M = Ga, In) with Et₄NSH/Et₄NSeH in acetonitrile gave [Et₄N]₃[In₃S₃Cl₆] · MeCN ( 3 ) (P2₁/c; a = 17.328(4) Å, b = 12.694(3) Å, c = 21.409(4) Å, β = 112.18(1)°, Z = 4), [Et₄N]₃[In₃Se₃Cl₆] · MeCN ( 4 ) (P2₁/c; a = 17.460(4) Å, b = 12.816(2) Å, c = 21.513(4) Å, β = 112.16(2)°, Z = 4), and [Et₄N]₃[Ga₃S₃Cl₆] · THF ( 5 ) (P2₁/n; a = 11.967(3) Å, b = 23.404(9) Å, c = 16.260(3) Å, β = 90.75(2)°, Z = 4). The [In₂SX₆]^2? anions (X = Cl, Br) in 1 and 2 consist of two InSX₃ tetrahedra sharing a common sulfur atom. The frameworks of 3, 4 and 5 each contain a six-membered ring of alternating metal and chalcogen atoms. Two terminal chlorine atoms complete a distorted tetrahedral coordination sphere around each metal atom.     

Die Pyridinaddukte der Goldhalogenide. 1. Darstellung und Struktur von [Hpy][AuCl4], AuCl3 · py, [AuCl2(py)2]Cl · H2O und [AuCl2(py)2][AuCl2]

Pyridine Adducts of the Gold Halides. 1. Synthesis and Structure of [Hpy][AuCl₄], AuC1₃ · py, [AuCl₂(py)₂]Cl · H₂O, and [AuCl₂(py)₂] [AuCl₂] HAuCl₄ reacts with pyridine in aqueous solution to form sparingly soluble [Hpy] [AuCl₄]. This goes into solution as [AuCl₂(py)₂]⁺ on adding an excess of pyridine. [Hpy][AuCl₄] decomposes above 195°C to HCl and AuCl₃ · py, which can also be obtained from NaAuCl₄ and pyridine. AuCl₂ · py is formed by the reaction of AuCl₂ · S(CH₂C₆H₄)₂ with pyridine in CHCl₃. According to the vibrational spectrum the complex is built up of trans[AuCl₂(py)₂]⁺ cations and [AuCl₂]^? anions. The IR spectra of [Hpy][AuCl₄], AuCl₃ · py, and [AuCl₂(py)₂]Cl · H₂O are discussed and assigned with respect to the crystal structures. [Hpy][AuCl₄] crystallizes monoclinic in the space group C2/m. In its structure alternating layers of [Hpy]⁺ cations and [AuCl₄]^? anions are observed. The monoclinic AuCl₃ · py (space group C2/c) consists of molecular complexes, wherein the gold atom is surrounded by three Cl atoms and one pyridine molecule in a square planar arrangement. The coordination is completed to an elongated octahedron by two more distant Cl atoms of neighbouring complexes. [AuCl₂(py)₂]Cl · H₂O crystallizes in the monoclinic space group P2₁/n. It forms planar trans[AuCl₂(py)₂]⁺ cations, weakly coordinated with an additional Cl^? ion and one H₂O molecule. The Au? Cl bond lengths in the complexes under investigation are in the range of 227 to 229 pm, the Au? N distances are between 197 and 199 pm.     

Gas-phase chemistry of electron deficient organometallic anions: the reactions of [Cr(CO)3]− ˙ and [Cr(CO)4]− ˙ with aldehydes,ketones, esters and ethers

Reactions in the gas phase of the 13- and 15-electron radical anions [Cr(CO)₃]^{? ˙} and [Cr(CO)₄]^{? ˙} with a series of 27 aldehydes, ketones, esters and ethers have been examined. Sequential alkane eliminations and metal-bonded CO ligand displacements were the principal reactions identified for the RCHO/[Cr(CO)₃]^{? ˙} systems with the latter reaction also common to the RCHO/[Cr(CO)₄]^{? ˙} systems. While [Cr(CO)₄]^{? ˙} was generally unreactive towards ketones R · R'CO, the principal products identified for [Cr(CO)₃]^{? ˙}/ketone reactions were the metal-decarbonylated species, respectively [R · R'CO · Cr(CO)_x]^{? ˙} with x = 0–3, and [R · (R' - H₂)CO · Cr(CO)₂]^{? ˙}. The reaction of [Cr(CO)₃]^{? ˙} with esters RCOOR' proceeds via metal insertion into the alkoxy C? O bond to give end products of the type [R'O · Cr · R(CO)₂]^? and [R'O? Cr(CO)₃]^? while the sole ionic products of dialkyl ether/[Cr(CO)₃]^{? ˙} reactions were identified as the alkoxytricarbonylchromium species [RO · Cr(CO)₃]^?.     

Die Kristallstrukturen der Hexachlorometallate NH4[SbCl6], NH4[WCl6], [K(18‐Krone‐6)(CH2Cl2)]2[WCl6]·6CH2Cl2 und (PPh4)2[WCl6]·4CH3CN

Crystal Structures of the Hexachlorometalates NH₄[SbCl₆], NH₄[WCl₆], [K(18‐crown‐6)(CH₂Cl₂)]₂[WCl₆]·6CH₂Cl₂ and (PPh₄)₂[WCl₆]·4CH₃CN The crystal structures of the title compounds were determined by single crystal X‐ray methods. NH₄[SbCl₆] and NH₄[WCl₆] crystallize isotypically in the space group C2/c with four formula units per unit cell. The NH₄⁺ ions occupy a twofold crystallographic axis, whereas the metal atoms of the [MCl₆]^— ions occupy a centre of inversion. There exist weak interionic hydrogen bridges. [K(18‐crown‐6)(CH₂Cl₂)]₂[WCl₆]·6CH₂Cl₂ crystallizes in the orthorhombic space group R3¯/m with Z = 3. The compound forms centrosymmetric ion triples, in which the potassium ions are coordinated with a WCl₃ face each. In trans‐position to it the chlorine atom of a CH₂Cl₂ molecule is coordinated so that, together with the oxygen atoms of the crown ether, coordination number 10 is achieved. (PPh₄)₂[WCl₆]·4CH₃CN crystallizes in the monoclinic space group P2₁/c with Z = 4. This compound, too, forms centrosymmetric ion triples, in which in addition the acetonitrile molecules are connected with the [WCl₆]^2— ion via weak C—H···Cl contacts.     

Charakterisierung von Distorsionsisomeren der Anionen Pentacyano-oxo-molybdat(IV) sowie Tetracyano-oxo-aqua-molybdat(IV) im festen Zustand. Kristallstrukturen von [(C6H5)4P]3[MoO(CN)5] · 7 H2O(grün), [(C6H5)4As]2 [MoO(OH2)(CN)4] · 4 H2O (blau) und [(C6H5)4P]2[MoO(OH2)(CN)4] · 4 H2O (grün)

Characterization of Distortional Isomers of the Anions Pentacyano-oxo-molybdate(IV) and of Tetracyano-aqua-oxo-molybdate(IV) in the Solid State. Crystal Structures of [(C₆H₅)₄P]₃[MoO(CN)₅] · 7 H₂O (green), [(C₆H₅)₄As]₂[MoO(OH₂)(CN)₄] · 4 H₂O (blue), and [(C₆H₅)₄P]₂[MoO(OH₂) (CN)₄] · 4 H₂O (green) Preparation of a series of salts containing the new pentacyano-oxo-molybdate(IV) anion is described: Cs₂H[MoO(CN)₅] (blue), [(CH₃)₄N]₂H[MoO(CN)₅] · 2 H₂O (blue) and [Cr(en)₃] [MoO(CN)₅] · 4 H₂O (green). The green [(C₆H₅)₄P]₃[MoO(CN)₅] · 7 H₂O crystallizes triclinic in the space group P1 . The molybdenum(IV) center is in an pseudo-octahedral environment of a terminal oxo-group (d(Mo?O); 1.705(4) Å), a CN^? group in the trans-position (d(Mo? C): 2.373(6) Å), and four equatorial CN^? groups (averaged d(Mo? C): 2.178 (Å). The blue and green salts exhibit v(Mo?O) stretching frequencies at 948 cm^?1 and 920 cm^?1, respectively. Blue and green salts containing the [MoO(OH₂)(CN)₄]^2? anion and [(C₆H₅)₄P]⁺ or [(C₆H₅)₄As]⁺ cations have been prepared and characterized by single crystal crystallography. [(C₆H₅)₄P]₂[MoO(OH₂)(CN)₄] · 4 H₂O (green) and [(C₆H₅)₄As]₂[MoO(OH₂)(CN)₄] · 4 H₂O (blue) crystallize monoclinic in the space group C—P2₁/n. They are considered to be distortional isomers of the complex anion: the green species has a Mo?O bond distance of 1.72(2) Å whereas for the blue species d(Mo?O) = 1.60(2) Å is found; the corresponding v(Mo?O) frequencies are at 920 cm^?1 and 980 cm^?1.