Molybdänhalogenidcluster mit sechs terminalen Alkoholatliganden: (C18H36N2O6Na)2[Mo6Cl8(OCH3)6] · 6CH3OH und (C18H36N2O6Na2)2[Mo6Cl8(OC6H5)6]

Molybdenum(II) Halide Clusters with six Alcoholate Ligands: (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₈(OCH₃)₆] · 6CH₃OH and (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₈(OC₆H₅)₆] . The reaction of Na₂[Mo₆Cl₈(OCH₃)₆] and 2,2,2-crypt yields (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₈(OCH₃)₆] · 6 CH₃OH ( 1 ), which is converted to (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₈(OC₆H₅)₆] ( 2 ) by metathesis with phenol. According to single crystal structure determinations ( 1 : P3 1c, a=14.613(3) Å, c=21.036(8) Å; 2 : P3 1c, a=15.624(1) Å, c=19.671(2) Å) the compounds contain anionic clusters [Mo₆Cl₈ⁱ(OR^a)₆]^2? ( 1 : d(Mo—Mo) 2.608(1) Å to 2.611(1) Å, d(Mo—Cl) 2.489(1) Å to 2.503(1) Å, d(Mo—O) 2.046(4) Å; 2 : d(Mo—Mo) 2.602(3) Å to 2.608(3) Å, d(Mo—Cl) 2.471(5) Å to 2.4992(5) Å, d(Mo—O) 2.091(14) Å). Electronic interactions of the halide cluster and the phenolate ligands in [Mo₆Cl₈(OC₆H₅)₆]^2? is investigated by means of UV/VIS spectroscopy and EHMO calculations.     

Reaktionen von Zinnchloriden mit Polysulfiden. Die Kristallstrukturen von (PPh4)2[SnCl2(S6)2], (PPh4)2[Sn4Cl4S5(S3)O] und (PPh4)2[SnCl6] · S8 · 2CH3CN

Reaction of Tin Chlorides with Polysulfides. Crystal Structures of (PPh₄)₂[SnCl₂(S₆)₂], (PPh₄)₂[Sn₄Cl₄S₅(S₃)O], and (PPh₄)₂[SnCl₆] · S₈ · 2CH₃CN . The reaction of PPh₄[SnCl₃] with Na₂S₄ in acetonitrile in the presence of small amounts of water yields (PPh₄)₂[Sn₄Cl₄S₅(S₃)O] and minor amounts of (PPh₄)₂[SnCl₂(S₆)₂], PPh₄Cl · 2S₈ and (PPh₄)₂[SnCl₆]. SnCl₄ is partially reduced by (PPh₄)₂S_x, PPh₄[SnCl₃] and (PPh₄)₂[SnCl₆] · S₈ · 2CH₃CN being produced. According to the X-ray crystal structure determination the [Sn₄Cl₄S₅(S₃)O]^2?-ion consists of an O atom that is coordinated by four Sn atoms which in turn are liked with one another by five single S atoms and one S₃ group. In the [SnCl₂(S₆)₂]^2?-ion the Sn atom is octahedrally coordinated by two Cl atoms in trans arrangement and by two chelating S₆ groups. Octahedral [SnCl₆]^2? ions and S₈ molecules in the crown conformation are present in (PPh₄)₄[SnCl₆] · S₈ · 2CH₃CN.     

(PPh4)[(ReO2S2)CuI] und (NEt4)2[(ReOS3)Cu3Cl4]: Fixierung der bisher nicht isolierten Ionen [ReO2S2]− und [ReOS3]− durch Ausnutzung der Stabilität der CuS2(Re)- und Cu3S3(Re)-Fragmente

(PPh₄)[(ReO₂S₂)CuI] and (NEt₄)₂[ReOS₃)Cu₃Cl₄]: Fixation of the up to now not Isolated Ions [ReO₂S₂]^? and [ReOS₃]^? Utilizing the Stability of the CuS₂(Re) and Cu₃S₃(Re) Fragments (PPh₄)[(ReO₂S₂)CuI] ( 1 ) and (NEt₄)₂[ReOS₃)Cu₃Cl₄] ( 2 ) containing the up to now not isolated oxothioperrhenate ions [ReO₂S₂]^? and [ReOS₃]^? as ligands, have been prepared by the reaction of (NEt₄)[ReS₄] with PPh₃ and CuI in acetone in the presence of (PPh₄)I (( 1 )) or with CuCl in CH₂Cl₂ in the presence of (NEt₄)Cl (( 2 )), respectively. 1 and 2 have been characterized by X-ray structure analysis, elemental analysis and spectroscopic studies (IR, UV/Vis). The electronic spectra show bands which can approximately be assigned to interesting low-energy charge-transfer-transitions of the type d(Cu) → d(Re). For crystal data see Inhaltsübersicht.     

Cyclothiazenokomplexe von Molybdän(V) und (VI), sowie von Wolfram(VI) Die Kristallstruktur von (PPh4)2[MoCl3(N3S2)]2 · 2 CH2Cl2

Cyclothiazeno Complexes of Molybdenum(V), Molybdenum(VI), and Tungsten(VI). Crystal Structure of (PPh₄)₂[MoCl₃(N₃S₂)]₂ · 2 CH₂Cl₂ . From excess trithiazylchloride and molybdenum or tungsten hexacarbonyl, respectively, the cyclothiazeno complexes [MCl₃(N₃S₂)]₂(S₂N₂) are obtained. They possess metal atoms linked via a planar S₂N₂ ring. The corresponding bromo compounds [MBr₃(N₃S₂)]₂(S₂N₂) can be obtained in liquid bromine from S₄N₄ and MoBr₄ or WBr₆, respectively, or from S₄N₄ with the corresponding metal hexacarbonyls in the presence of bromine. Thermolysis of [WBr₃(N₃S₂)]₂(S₂N₂) yields [WBr₃(N₃S₂)]₂ which is dimerized via nitrogen bridges. When [MoCl₃(N₃S₂)]₂(S₂N₂) reacts with tetraphenylphosphonium chloride in dichloromethane, the S₂N₂ acts as reducing agent, and the paramagnetic molybdenum(V) complex (PPh₄)₂[MoCl₃(N₃S₂)]₂ · 2 CH₂Cl₂ is obtained (μ_eff = 1.2 B.M.). The i.r. spectra are reported. The crystal structure of (PPh₄)₂[MoCl₃(N₃S₂)]₂ · 2 CH₂Cl₂ was determined by X-ray diffraction (2524 independent reflexions, R = 0.052). It crystallizes in the space group P1 with the lattice con- stants a = 943.9, b = 1209.6, c = 1469.2 pm, α = 69.27, β = 72.20 and γ = 82.08°, Z = 1. There are tetraphenylphosphonium cations and centrosymmetric, dimeric anions [MoCl₃(N₃S₂)]₂^2?. The molybdenum atoms are part of six-membered cyclothiazeno rings MoN₃S₂ with MoN bond lengths of 177 and 197 pm; the N atom with the longer MoN bond is linked to the second Mo atom, so that a planar Mo₂N₂ ring results; this ring is nearly coplanar with the two MoN₃S₂ rings. Furthermore, each molybdenum atom is linked with three chlorine atoms with MoCl bond lengths of 240–242 pm, so that the Mo atoms possms a distorted octahedral coordination.     

Molybdän‐ und Wolfram‐Komplexe mit MNS‐Sequenzen. Die Kristallstrukturen von [MoCl3(N3S2)(1,4‐Dioxan)2] und [Mo2Cl2(μ‐NSN)2(μ‐O)(NCMe3)(OCMe3)2]2

Molybdenum and Tungsten Complexes with MNS Sequences. Crystal Structures of [MoCl₃(N₃S₂)(1,4‐dioxane)₂] and [Mo₂Cl₂(μ‐NSN)₂(μ‐O)(NCMe₃)(OCMe₃)₂]₂ The cyclo‐thiazeno complexes [Cl₃MNSNSN]₂ of molybdenum and tungsten react with 1,4‐dioxane in dichloromethane suspension to give the binuclear donor‐acceptor complexes [μ‐(1,4‐dioxane){MCl₃(N₃S₂)}₂] which are characterized by IR spectroscopy. With excess 1,4‐dioxane the molybdenum compound forms the complex [MoCl₃(N₃S₂)(1,4‐dioxane)₂] in which, according to the crystal structure determination, one of the dioxane molecules coordinates at the molybdenum atom, the other one at one of the sulfur atoms of the cyclo‐thiazeno ring. The μ‐(NSN^2–) complex [Mo₂Cl₂(μ‐NSN)₂(μ‐O)(NCMe₃)(OCMe₃)₂]₂ has been obtained by the reaction of [MoN(OCMe₃)₃] with trithiazyle chloride in carbontetrachloride solution. According to the crystal structure determination this compound forms centrosymmetric dimeric molecules via two of the nitrogen atoms of two of the μ‐(NSN) groups to give a Mo₂N₂ fourmembered ring. [MoCl₃(N₃S₂)(1,4‐dioxane)₂]: Space group P2₁/c, Z = 4, lattice dimensions at –70 °C: a = 1522.9(2); b = 990.3(1); c = 1161.7(1) pm; β = 106.31(1)°, R₁ = 0.0317. [Mo₂Cl₂(μ‐NSN)₂(μ‐O)(NCMe₃)(OCMe₃)₂]₂ · 4 CCl₄: Space group P2₁/c, Z = 2, lattice dimensions at –83 °C: a = 1216.7(1); b = 2193.1(2); c = 1321.8(1) pm; β = 98.23(1)°; R₁ = 0.0507.     

A Rare Tetranuclear Thorium(IV) μ4‐Oxo Cluster and Dinuclear Thorium(IV) Complex Assembled by Carbon–Oxygen Bond Activation of 1,2‐Dimethoxyethane (DME)

The synthesis and X‐ray crystal structure of two new multinuclear thorium complexes are reported. The tetranuclear μ₄‐oxo cluster complex Th₄(μ₄‐O)(μ‐Cl)₂I₆[κ²(O,O’)‐μ‐O(CH₂)₂OCH₃]₆ and the dinuclear complex Th₂I₅[κ²(O,O’)‐μ‐O(CH₂)₂OCH₃]₃(DME) (DME=dimethoxyethane) are formed by C?O bond activation of 1,2‐dimethoxyethane (DME) mediated by thorium iodide complexes.     

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.     

Über die Umsetzung von P4E3I2 (E = S,Se) mit einigen Carbonsäuren und Dithiocarbonsäuren

On the Reaction of P₄E₃I₂ (E = S, Se) with some Carboxylic Acids and Dithiocarbamic Acids By the reaction of α-P₄E₃I₂ (E = S, Se) with carboxylic acids, dithiobenzoic acid or dithiocarbamic acids in the presence of triethylamin or with (C₆H₅)₃SnR, or of β-P₄E₃I₂ with tin-organic compounds α-P₄E₃(I)R, α(β)-P₄E₃R₂ [R = ? OC(O)C₆H₅, ? OC(O)CH₃, ? SC(S)NC₅H₁₀, ? SC(S)N(C₂H₅)₂], α-P₄S₃(I)SC(S)C₆H₅, α-P₄S₃(SC(S)C₆H₅)₂ and β-P₄E₃(I)R (R = ? OC(O)C₆H₅, ? OC(O)CH₃) were prepared in solution and identified by ³¹P NMR spectroscopy. In addition α-P₄S₃(NC₅H₁₀)(SC(S)NC₅H₁₀) was detected. The β-isomers could be obtained also with lesser yields by the reaction with the dithiocarbamic acids, too. The substitution of the second iodine ligand in β-P₄E₃I₂ resulted mainly in β-P₄S₃(R_exo)₂ and by inversion of the configuration at a phosphorus atom, in β-P₄E₃R_exoR_endo. α-P₄S₃I₂ reacted with methanol in CS₂ to α-P₄S₃(OCH₃)(SC(S)OCH₃) and α-P₄S₃(SC(S)OCH₃)₂. The ³¹P NMR data of the compounds are discussed. The ³¹P NMR spectra of the α(β)-P₄E₃ dithiocarbamates indicate dynamic processes in the solution, e. g. α-P₄S₃(I)(SC(S)NR₂) showed an intramolecular conversion, due to the anisobidentate dithiocarbamate ligand. This behaviour had not previously been noticed for compounds with a P₄S₃-skeleton.     

Synthesis and Structural Characterization of Six Pentanuclear and Tetranuclear Mo/W‐Cu‐S Clusters with Bis(diphenylphosphanyl) Methane

Six heterothiometalic clusters, namely, [WS₄Cu₄(dppm)₄](ClO₄)₂ · 2DMF · MeCN ( 1 ), [MoS₄Cu₄(dppm)₄](NO₃)₂ · MeCN ( 2 ) [MoS₄Cu₃(dppm)₃](ClO₄) · 4H₂O ( 3 ), [WS₄Cu₃(dppm)₃](NO₃) · 4H₂O ( 4 ), [WS₄Cu₃(dppm)₃]SCN · CH₂Cl₂ ( 5 ), and [WS₄Cu₃(dppm)₃]I · CH₂Cl₂ ( 6 ) [dppm = bis (diphenylphosphanyl)methane] were synthesized. Compounds 1 – 4 were obtained by the reactions of (NH₄)₂MS₄ (M = Mo, W) with [Cu₂(μ₂‐dppm)₂(MeCN)₂(ClO₄)₂] {or [Cu(dppm)(NO₃)]₂} in the presence of 1,10‐phen in mixed solvent (CH₃CN/CH₂Cl₂/DMF for 1 and 2 , CH₂Cl₂/CH₃OH/DMF for 3 and 4 . Compounds 5 and 6 were obtained by one‐pot reactions of (NH₄)₂WS₄ with dppm and CuSCN (or CuI) in CH₂Cl₂/CH₃OH. These clusters were characterized by single‐crystal X‐ray diffraction as well as IR, ¹H NMR, and ³¹P NMR spectroscopy. Structure analysis showed that compounds 1 and 2 are “saddle‐shaped” pentanuclear cationic clusters, whereas compounds 3 – 6 are “flywheel‐shaped” tetranuclear cationic clusters. In 1 and 2 , the MS₄^2– unit (M = W, Mo) is coordinated by four copper atoms, which are further bridged by four dppm molecules. In compounds 3 – 6 , the MS₄^2– unit is coordinated by three copper atoms and each copper atom is bridged by three dppm ligands.     

Komplexbildung des tert-Butyliminovanadium(V)-trichlorids mit O-Donor-Liganden

Coordination Compounds of tert-Butyliminovanadium(V) Trichloride with O-Donor-Ligands The reaction of tert-butyliminovanadium(V)trichloride ( 1 ) with cyclic and acyclic ethers, ethylene carbonate and thietane has been studied. The 1:1-complexes have a different stability; reversible and irreversible cleavage of ether in the coordination sphere of the vanadium atom rearranging in ω-chloroalkanolato ligands are observed. The reaction of 1 with 2-chloroethanol, 3-chloropropanol and 5-chloropentanol yields the complexes ^tC₄H₉N = V(OR)Cl₂ (R = CH₂CH₂CH₂CH₂CH₂Cl) and [^tC₄H₉N = V(OR)Cl₂ · ROH]; in the presence of triethylamine the disubstituted compounds ^tC₄H₉N = V(OR)₂Cl are formed. The ⁵¹V NMR spectra are discussed. The crystal structure of [^tC₄H₉N = VCl₃ · DME] ( 12 ) and [^tC₄H₉N = V(OCH₂CH₂Cl)Cl₂ · HOCH₂CH₂Cl] ( 13 ) has been determined. The vanadium atoms in 13 have a distorted octahedral coordination and are linked by the oxygen atoms of the 2-chloroethanolato ligands forming a binuclear complex. In solution molecular weight measurement and ⁵¹V NMR data indicate the equilibrium between a mononuclear complex 13 and its isomer [^tC₄H₉N = V(OCH₂CH₂Cl)₂Cl · HCl].     

Synthesis and Structural Characterization of Singly,Doubly, and Triply Bridged Derivatives of Hexachlorocyclotriphosphazene with Bis(2-hydroxyethyl) Ether and 2,2-dimethylpropane-1,3-diol

Abstract

The reactions of hexachlorocyclotriphosphazene, N₃P₃Cl₆ (1), with 2,2-dimethylpropane-1,3-diol (2), and bis(2-hydroxyethyl) ether (3) have been previously reported. Although both reactions gave the expected spiro, ansa, and bridged type products, open-chain and triply bridged derivatives from both systems and singly bridged derivatives from 2,2-dimethylpropane-1,3-diol (2) were not isolated, and doubly bridged compounds were only detected in trace amounts in both systems. However, in a subsequent reinvestigation in tetrahydrofuran (THF) solution, the reaction of 1 with the diols 2 and 3 gave the open chain compounds N₃P₃Cl₅[O(CH₂)₂CMe₂OH] (4) and N₃P₃Cl₅[(OCH₂CH₂)₂OH] (5), the singly bridged compound N₃P₃Cl₅[(OCH₂)₂-CMe₂]N₃P₃Cl₅ (6), the doubly bridged compounds N₃P₃Cl₄[(OCH₂)₂CMe₂]₂N₃P₃Cl₄ (8) and N₃P₃Cl₄[(OCH₂CH₂)₂O]₂N₃P₃Cl₄ (9), and the triply bridged compounds N₃P₃Cl₃[(OCH₂)₂-CMe₂]₃N₃P₃Cl₃ (10) and N₃P₃Cl₃[(OCH₂CH₂)₂O]₃N₃P₃Cl₃ (11).

The doubly bridged derivatives were also isolated in better yields relative to earlier reports. The substituted cyclotriphosphazenes have been characterized by elemental analysis, mass spectrometry, as well as by ¹H, ³¹P, and ¹³C NMR spectroscopy. It is found that with variation of the solvent there is a decrease in the product formed by intramolecular reactions (spiro and ansa derivatives) and a concomitant increase in the amount of products formed by intermolecular reactions (singly, doubly, and triply bridged derivatives) of cyclophosphazene.     

Isomere η2-Acyl- und σ-Alkyl(carbonyl)-Komplexe von Molybdän und Wolfram. Eine Studie zum Bildungs-mechanismus,zur Isomerisierungsgeschwindigkeit und zur Steuerung der Gleichgewichtslage

η²-Acyl and σ-Alkyl(carbonyl) Coordination in Molybdenum and Tungsten Complexes: Synthesis and Studies of the Isomerization Equilibria and Kinetics The anionic molybdenum and tungsten complexes [L_RM(CO)₃]^? (L_R^? = [(C₅H₅)Co{P(O)R₂}₃]^?, R = OCH₃, OC₂H₅, O-i-C₃H₇; M = Mo, W) have been alkylated with the iodides R′ I, R′ = CH₃, C₂H₅, i-C₃H₇, and CH₂C₆H₅. The reactivity pattern of the alkylation is in accord with a S_N2 mechanism. Depending on M, R′, reaction temperature, and time the η-alkyl (carbonyl) compounds [L_RM(CO)₃R′] and/or the isomeric η²-acyl compounds [L_RM(CO)₂(η²-COR′)] can be obtained. 8 new σ-alkyl(carbonyl) compounds and 15 new η²-acyl compounds have been isolated and characterized. The ¹H NMR and the IR spectra give conclusive evidence that the σ-alkyl(carbonyl) compounds [L_RM(CO)₃R′] are formed as the primary products of the alkylation and that they isomerize partly or completely to give the η²-acyl compounds [L_RM(CO)₂(η²-COR′)]. The position of the equilibrium σ-alkyl(carbonyl)/η²-acyl is controlled by the steric demands of the groups R′ and the ligands L_R^?. The molybdenum compounds isomerize much more readily than the tungsten compounds. The rate constants of the isomerization processes [L_RMo(CO)₃CH₃] → [L_RMo(CO)₂(η²-COCH₃)], R = OCH₃, OC₂H₅, and O-i-C₃H₇, measured at 305 K in acetone-d₆, are 6–8 x 10^?3 s^?1.     

AsPh4[W2Cl4(N3S2)3] · CCl4; Synthese und Kristallstruktur

AsPh₄[W₂Cl₄(N₃S₂)₃] · CCl₄; Synthesis and Crystal Structure The title compound was obtained in form of black crystals along with other products by the reaction of H₂S and AsPh₄[WCl₄(N₃S₂)] in dichloromethane and subsequent addition of CCl₄. Its crystal structure was determined by X-ray diffraction (3036 observed reflexions, R = 0.051). Crystal data: triclinic, space group P¯1, Z = 2, a = 1369, b = 1398, c = 1441 pm, α = 64.8, β = 68.02 and γ = 58.1°. The compound consists of AsPh₄^⊕ ions, CCl₄ molecules and [W₂Cl₄(N₃S₂)₃]^? ions. In the latter, one tungsten atom is member of one planar WN₃S₂ ring while the second tungsten atom belongs to two such rings forming a nearly planar S₂N₃WN₃S₂ unit. Two nitrogen atoms of this unit are linked to the other tungsten atom forming a WN₂W ring. Two chloro ligands at each tungsten atom complete the coordination sphere to coordination numbers of six.     

Darstellung von Trifluormethylhalogen-Iodaten(I) des Typs (CH3)4N+CF3IX− (X = F,Cl, Br) und Trifluormethyltrifluormethoxyiodat(I) (CH3)4N+CF3IOCF3−

Preparation of Trifluormethylhalogen Iodate(I) Salts (CH₃)₄N⁺CF₃IX^? (X = F, Cl, Br) and Trifluormethyltrifluormethoxy Iodate(I) (CH₃)₄N⁺CF₃IOCF₃^? We describe the preparation of new trifluormethyliodate(I) salts CF₃IX^? (X = F, Cl, Br, OCF₃). (CH₃)₄N⁺CF₃ICl^? and (CH₃)₄N⁺CF₃IBr^? are obtained via addition of CF₃I with the corresponded tetramethylammonium halogenide. (CH₃)₄N⁺CF₃IOCF₃^? is synthesized by comproportionation of (CH₃)₄N⁺CF₃ICl^? with CF₃OCl under formation of Cl₂ at ?78°C. (CH₃)₄N⁺CF₃IF^? is formed either, through thermolysis of (CH₃)₄N⁺ CF₃IOCF₃^? under separation of COF₂, or reaction of CF₃I with (CH₃)₄N⁺ OCF₃^?. The thermolabile compounds have been characterized by i.r., Raman, ¹⁹F-, ¹³C NMR spectroscopy.     

A novel dinuclear bismuth(III) coordination compound: bis(μ‐pyridine‐2,6‐dicarboxylato)‐κ4O2,N,O6:O6′;κ4O2:O2′,N,O6‐bis[(azido‐κN)(1,10‐phenanthroline‐κ2N,N′)bismuth(III)] tetrahydrate

A novel dinuclear bismuth(III) coordination compound, [Bi₂(C₇H₃NO₄)₂(N₃)₂(C₁₂H₈N₂)₂]·4H₂O, has been synthesized by an ionothermal method and characterized by elemental analysis, energy‐dispersive X‐ray spectroscopy, IR, X‐ray photoelectron spectroscopy and single‐crystal X‐ray diffraction. The molecular structure consists of one centrosymmetric dinuclear neutral fragment and four water molecules. Within the dinuclear fragment, each Bi^III centre is seven‐coordinated by three O atoms and four N atoms. The coordination geometry of each Bi^III atom is distorted pentagonal–bipyramidal (BiO₃N₄), with one azide N atom and one bridging carboxylate O atom located in axial positions. The carboxylate O atoms and water molecules are assembled via O—H...O hydrogen bonds, resulting in the formation of a three‐dimensional supramolecular structure. Two types of π–π stacking interactions are found, with centroid‐to‐centroid distances of 3.461 (4) and 3.641 (4) Å.     

Reaction of [P3N3Cl4(NH2)2] with [HN(POCl2)2]; The crystal structure of the phosphazenium salt [P3N3HCl4(NH2)2]+[N(POCl2)2]−

The reaction of diaminotetrachloro-cyclotriphosphazene with tetrachloride of μ-imino-diphosphoric acid leads to the formation of the salt-like compound [P₃N₃HCl₄(NH₂)₂]⁺[N(POCl₂)₂]⁻ which identity was unambiguously established by means of X-ray structure analysis. The structure is composed of [P₃N₃HCl₄(NH₂)₂]⁺ cations and [N(POCl₂)₂]⁻ anions joined by a system of H-bonds. As in other phosphazenium salts, the protonation of the ring N atom leads to significant changes in the endocyclic P N bond lengths.     

Darstellung und Kristallstrukturen von Silber(I)-Gemischtligandkomplexen mit Bibenzimidazol und Triphenylphosphan: [Ag(PPh3)2(bbimH2)](COOCH3) · 2 CH2Cl2 und [{Ag(PPh3)2}2(μ-bbim)] · 4 CH2Cl2

Preparation and Crystal Structures of Silver(I) Mixed Ligand Complexes with Bibenzimidazole and Triphenylphosphane: [Ag(PPh₃)₂(bbimH₂)](COOCH₃) · 2 CH₂Cl₂ and [{Ag(PPh₃)₂}₂(μ-bbim)] · 4 CH₂Cl₂ The title compounds are obtained from silver acetate, 2,2′-bibenzimidazole and PPh₃. They are characterized by their IR, ¹H-NMR, ³¹P-NMR spectra and crystal structure determinations. [Ag(PPh₃)₂(bbimH₂)](COOCH₃) · 2 CH₂Cl₂: Reaction in CH₂Cl₂. Space group C2/c, Z = 4, 3129 observed unique reflections, R = 0.033. Lattice parameters at 203 K: a = 1450.8; b = 1556.2; c = 2316.4 pm; β = 99.69°. The crystal structure is built up by monomeric molecules with distorted tetrahedral coordination of the silver atom (AgP₂N₂) and bibenzimidazole as a bidentate ligand. The acetate ion is linked to the NH-groups of the bibenzimidazole by hydrogen bonds. [{Ag(PPh₃)₂}₂(μ-bbim)] · 4 CH₂Cl₂: Reaction in fused PPh₃ at 180 °C. Space group P 1, Z = 1. 9227 observed unique reflections, R = 0.051. Lattice parameters at 203 K: a = 1276.5; b = 1352.1; c = 1408.1 pm; α = 96.97; β = 115.87; γ = 96.84°. The crystal structure is built up by centrosymmetric molecules with distorted tetrahedral coordination of the silver atoms (AgN₂P₂) and bibenzimidazolate(2–) as tetradentate bridging ligand.     

Drei Heterocubanartige (MII4O4)‐Typ Verbindungen (M = FeII,CoII, NiII)

By reaction of M^IICl₂·x H₂O (M = Fe (x = 4), Co, Ni (x = 6)) and LiOH·H₂O in diethylene glycol (DEG) rod‐like crystals of the composition M^II₄Cl₄(OCH₂CH₂OCH₂CH₂OH)₄ are formed. According to X‐ray diffraction data obtained by both, single crystals and powders, the Co^II and Ni^II compounds crystallize monoclinic with C2/c (Co^II₄Cl₄(OCH₂CH₂OCH₂CH₂OH)₄ ( 1 ): a = 2084.1(4), b = 919.0(2), c = 1754.0(4) pm, β = 124.3(1)°, Z = 4; Ni^II₄Cl₄(OCH₂CH₂OCH₂CH₂OH)₄ ( 2 ): a = 2055.2(4), b = 932.1(2), c = 1727.4(4) pm, β = 125.2(1)°, Z = 4), whereas Fe^II₄Cl₄(OCH₂CH₂OCH₂CH₂OH)₄ ( 3 ) crystallizes tetragonal with (a = 1251.4(2), c = 915.3(2) pm, Z = 2). All compounds exhibit analogous molecular structures which are built of a heterocubane‐type core consisting of four metal ions and four deprotonated oxygen atoms of four coordinated diethylene glycol molecules. Neutrality of charge is realized by additional coordination of four chloride anions. In addition to the structural characterization, the thermal and magnetical properties of the title compounds are investigated in detail.     

Kristall- und Molekülstruktur von fac-Trichloro-tris(dimethylsulfoxid)bismut(III) BiCl3(DMSO)3

Crystal and Molecular Structure of fac-Trichloro-tris(dimethyl sulfoxide)bismuth(III) BiCl₃(DMSO)₃ Crystals of the known, although structurally not characterized title compound were fortuitously obtained from a reaction mixture containing (CH₃)₃SiN(SO₂CH₃)₂, BiCl₃, DMSO, CH₂Cl₂ and CH₃NO₂. Crystallographic data (at ?130°C): triclinic, space group P1 1, a = 816.1(5), b = 885.1(6), c = 1 360.6(8) pm, α = 77.58(3), β = 77.39(3), γ = 64.42(3)°, U = 0.8569 nm³, Z = 2. The DMSO ligands are bound through oxygen to the Bi atom. Important bond distances and angles in the resulting fac-octahedral complex are as follows: Bi? Cl 258.9, 261.0, 263.0, Bi? O 242.6, 245.7, 246.1 pm; Cl? Bi? O (trans) 170.3, 170.6, 176.9, Cl? Bi? Cl 94.6, 94.7, 96.0, O? Bi? O 81.7, 85.4, 87.9, Cl? Bi? O (cis) in the range 87.2–92.6, Bi? O? S 123.4, 126.1, 129.6°.     

Synthesis and Crystal Structures of Cs5Nb2S4X9 – Double Salts Containing New Cluster Anions [Nb2(μ-S2)2X8]4– (X = Cl,Br)

Bis(disulfide)bridged Nb(+4) cluster halide complexes [Nb₂S₄X₈]^4– (X = Cl, Br) were prepared by acid hydrolysis of [Nb₂S₄(NCS)₈]^4– in concentrated aqueous HCl or HBr, solution from which they can be isolated as double salts Cs₅[Nb₂S₄X₈]X (X = Cl, 1 ; X = Br, 2 ). The crystal structures of 1 and 2 were determined. The isolation and X-ray structure of oxonium salt (H₃O)₅ [Nb₂S₄Cl₈]Cl ( 3 ) is also reported. 1 – 3 contain new [Nb₂S₄X₈]^4– anions which can also be viewed as excised building blocks of polymeric solids NbS₂X₂. The extra halogen resides in the center of octahedron formed by six Cs⁺ or H₃O⁺ ions. All the three salts are isostructural and crystallize in tetragonal space group Immm with the following parameters: a = 10.269(2), b = 16.343(2), c = 7.220(1) Å for 1 , a = 10.934(1), b = 16.613(2), c = 7.470(1) Å for 2 , a = 9.639(1), b = 16.031(1), c = 7.071(1) Å for 3 . The parameters of the Nb₂S₄ core are only slightly affected by the change from Cl to Br.