Hexatellurium Rings in Coordination Polymers and Molecular Clusters: Synthesis and Crystal Structures of [M(Te6)]X3 (M = Rh,Ir; X = Cl,Br, I) and [Ru2(Te6)](TeBr3)4(TeBr2)2

The reaction of an electron‐rich transition metal M (M = Ru, Rh, Ir), tellurium and TeX₄ (X = Cl, Br, I) resulted in black crystals of five ternary coordination polymers with the general composition [M^III(Te₆)]X₃ (M = Rh, Ir) and of the molecular cluster compound [Ru^II₂(Te₆)](Te^IIBr₃)₄(Te^IIBr₂)₂. X‐ray diffraction on single‐crystals revealed that the compounds [M(Te₆)]X₃ crystallize isostructurally in the trigonal space group type R$\bar{3}$ c. In their crystal structures linear, positively charged [M^III(Te₆)] chains form the motif of a hexagonal rod packing. In the chain, each of the formally uncharged Te₆ molecules with chair conformation acts as a bis‐tridentate bridging ligand to two M atoms. The octahedrally coordinated M atoms are spiro atoms in the chain of trans vertices sharing heterocubane fragments. Including the isolated halide ions, which provide charge balance, the entire arrangement resembles a cut‐out of the α‐polonium structure type.In the monoclinic compound Ru₂Te₁₂Br₁₆ (space group P2₁/n), the ruthenium atoms of the hetero‐cubane core of the molecular cluster [Ru₂(Te₆)](TeBr₃)₄(TeBr₂)₂ are saturated by terminal bromidotellurate(II) groups. Again, the Te₆ ring is formally uncharged. With the tellurium atoms acting as electron‐pair donors the 18 electron rule is fulfilled for the M atoms in all compounds.     

Neutral tellurium rings in the coordination polymers [Ru(Te9)](InCl4)2, [Ru(Te8)]Cl2, and [Rh(Te6)]Cl3

Shiny black, air‐insensitive crystals of tellurium‐rich one‐dimensional coordination polymers were synthesized by melting a mixture of the elements with TeCl₄. The compounds [Ru(Te₉)](InCl₄)₂ and [Ru(Te₈)]Cl₂ crystallize in the monoclinic space group type C2/c, whereas [Rh(Te₆)]Cl₃ adopts the trigonal space group type R$\bar 3Shiny black, air-insensitive crystals of tellurium-rich one-dimensional coordination polymers were synthesized by melting a mixture of the elements with TeCl(4). The compounds [Ru(Te(9))](InCl(4))(2) and [Ru(Te(8))]Cl(2) crystallize in the monoclinic space group type C2/c, whereas [Rh(Te(6))]Cl(3) adopts the trigonal space group type R ?3c. In the crystal structures, linear, positively charged [M(m+) (Te(n)(±0))] (M=Ru, m=2; Rh, m=3) chains run parallel to the c axes. Each of the uncharged Te(n) molecules (n=6, 8, 9) coordinates two transition-metal atoms as a bridging bis-tridentate ligand. Because the coordinating tellurium atoms act as electron-pair donors, the 18-electron rule is fulfilled for the octahedrally coordinated transition-metal cations. Based on DFT calculations, the quantum theory of atoms in molecules (QTAIM) and the electron localizability indicator (ELI) provide insight into the principles of the polar donor bonding in these complexes. Comparison with optimized ring geometries reveals substantial tension in the coordinating tellurium molecules.     

Neue Halogenochalkogen(IV)‐Säuren: [H3O(Benzo‐18‐Krone‐6)]2[Te2Br10] und [H5O2(Dibenzo‐24‐Krone‐8)]2[Te2Br10]

Novel Halogenochalcogeno(IV) Acids: [H₃O(Benzo‐18‐Crown‐6)]₂[Te₂Br₁₀] and [H₅O₂(Dibenzo‐24‐Crown‐8)]₂[Te₂Br₁₀] Systematic studies on halogenochalcogeno(IV) acids containing tellurium and bromine led to the new crystalline phases [H₃O(Benzo‐18‐Crown‐6)]₂[Te₂Br₁₀] ( 1 ) and [H₅O₂(Dibenzo‐24‐Crown‐8)]₂[Te₂Br₁₀] ( 2 ). The [Te₂Br₁₀]^2‐ anions consists of two edge‐sharing distorted TeBr₆ octahedra, the oxonium cations are stabilized by crownether. ( 1 ) crystallizes in the monoclinic space group P2₁/n with a = 14.520(5) Å, b = 22.259(6) Å, c = 16.053(5) Å, β = 97.76(3)° and Z = 4, whereas ( 2 ) crystallizes in the triclinic space group with a = 11.005(4) Å, b = 12.103(5) Å, c = 14.951(6) Å, α = 71.61(3)°, β = 69.17(3)°, γ = 68.40(3)° and Z = 1.     

Isotype Strukturen einiger Hexaamminmetall(II)-halogenide von 3d-Metallen: [V(NH3)6]I2, [Cr(NH3)6]I2, [Mn(NH3)6]Cl2, [Fe(NH3)6]Cl2, [Fe(NH3)6]Br2, [Co(NH3)6]Br2 und [Ni(NH3)6]Cl2

The Structures of some Hexaammine Metal(II) Halides of 3 d Metals: [V(NH₃)₆]I₂, [Cr(NH₃)₆]I₂, [Mn(NH₃)₆]Cl₂, [Fe(NH₃)₆]Cl₂, [Fe(NH₃)₆]Br₂, [Co(NH₃)₆]Br₂ and [Ni(NH₃)₆]Cl₂ Crystals of yellow [V(NH₃)₆]I₂ and green [Cr(NH₃)₆]I₂ were obtained by the reaction of VI₂ and CrI₂ with liquid ammonia at room temperature. Colourless crystals of [Mn(NH₃)₆]Cl₂ were obtained from Mn and NH₄Cl in supercritical ammonia. Colourless transparent crystals of [Fe(NH₃)₆]Cl₂ and [Fe(NH₃)₆]Br₂ were obtained by the reaction of FeCl₂ and FeBr₂ with supercritical ammonia at 400°C. Under the same conditions orange crystals of [Co(NH₃)₆]Br₂ were obtained from [Co₂(NH₂)₃(NH₃)₆]Br₃. Purple crystals of [Ni(NH₃)₆]Cl₂ were obtained by the reaction of NiCl₂ · 6H₂O and NH₄Cl with aqueous NH₃ solution. The structures of the isotypic compounds (Fm3 m, Z = 4) were determined from single crystal diffractometer data (see “Inhaltsübersicht”). All compounds crystallize in the K₂[PtCl₆] structure type. In these compounds the metal ions have high-spin configuration. The orientation of the dynamically disordered hydrogen atoms of the ammonia ligands is discussed.     

Cs2[Pr6(C2)]I12 - das erste quaternäre reduzierte Halogenid mit isolierten [M6(C2)]-Clustern

Cs₂[Pr₆(C₂)]I₁₂ — the First Quaternary Reduced Halide with Isolated [M₆(C₂)] Clusters . Cs₂[Pr₆(C₂)]I₁₂ is obtained as one of the major products from the reaction of PrI₃, cesium and carbon in sealed tantalum containers at 850°C. The crystal structure triclinic, P 1 ; a=948.1(2), b=953.6(3), c=1 005.2(3) pm; α=71.01(2); β=84,68(3), γ=89.37(2)°; Z=1 contains discrete Pr₆I₁₂-type clusters elongated along the pseudo-four-fold axis to accommodate the C₂ units (d(C—C)=139 pm). The clusters are connected through common ^i?aI and ^a?iI linkages at metal vertices and edges according to Cs₂[Pr₆(C₂)ⁱI₆^i?aI_6/2]^a?iI_6/2. The cesium cations occupy interstices within the (distorted) iodide layers in a way that “Cs₂I₁₈” dimers are formed, in which Cs⁺ is surrounded by eleven I^?. On the basis of the MO scheme of [Sc₆(C₂]I₁₁, the bonding of the C² unit is discussed and compared with other cluster compounds containing C₂ units.     

Crystal Structure of [M(NH3)5Cl]2[IrCl6]Cl2 (M = Co, Rh, Ir) Binary Complex Salts

Binary complex salts of M(NH₃)₅Cl]₂[IrCl₆]Cl₂ composition, where M = Co(III), Rh(III), or Ir(III), have been studied. All phases are isostructural with [M(NH₃)₅Cl]₂[PtCl₆]Cl₂ complexes [M = Rh(III) and Ir(III)]; Xray structural and crystallochemical analysis have been performed.     

Synthesis and Crystal Structure of Bis(methyltriethylammonium) Hexabromotellurate(IV)‐tris{dibromodiselenate(I)}, [NMeEt3]2n[TeBr6(Se2Br2)3]n,Containing a Chain‐Polymeric Mixed‐valence Bromotellurate(IV)‐Selenate(I) Anion

Red crystals of [NMeEt₃]_2n[TeBr₆(Se₂Br₂)₃]n ( 1 ) were isolated when selenium and bromine (1:1) were allowed to react in acetonitrile solution in the presence of tellurium(IV) bromide and methyltriethylammonium bromide (1:2). The salt 1 crystallizes in the monoclinic space group C2/c with the cell dimensions a = 27.676(6) Å, b = 9.665(2) Å, c = 18.796(4) Å and ß = 124.96(3)° (120 K). The [TeBr₆(Se₂Br₂)₃]^2— anions contain nearly regular octahedral [TeBr₆]^2— ions which are incorporated into a polymeric chain by bonding contacts between 3 facial bromo ligands and 3 Se₂Br₂ molecules, one of which is situated on the twofold symmetry axis. The distances between the μBr ligands and the Se^I atoms of the Se₂Br₂ molecules are observed in the range 3.308(2) — 3.408(2) Å and can tentatively be interpreted as donor‐acceptor bonds with μBr as donors and Se₂Br₂ as acceptors. The Te^IV—Br distances are in the range 2.669(1) — 2.687(1) Å. The bond lengths in the connecting Se₂Br₂ molecules are: Se^I—Se^I = 2.267(2) and 2.281(2) Å, Se^I—Br = 2.340(1), 2.353(1) and 2.337(1) Å.     

Modified Tellurium Subhalides in the New Structure Type [Te15X4]n[MOX4]2n (M = Mo,W; X = Cl,Br)

The reactions of Te₂Br with MoOBr₃, TeCl₄ with MoNCl₂/MoOCl₃, and Te with WBr₅/WOBr₃ yield black, needle-like crystals of [Te₁₅X₄][MOX₄]₂ (M = Mo, W; X = Cl, Br). The crystal structure determinations [Te₁₅Br₄][MoOBr₄]₂: monoclinic, Z = 1, C2/m, a = 1595.9(4) pm, b = 403.6(1) pm, c = 1600.4(4) pm, β = 112.02(2)°; [Te₁₅Cl₄][MoOCl₄]₂: C2/m, a = 1535.3(5) pm, b = 402.8(2) pm, c = 1569.6(5) pm, β = 112.02(2)°; [Te₁₅Br₄][WOBr₄]₂: C2, a = 1592.4(4) pm, b = 397.5(1) pm, c = 1593.4(5) pm, β = 111.76(2)° show that all three compounds are isotypic and consist of one-dimensional ([Te₁₅X₄]²⁺)_n and ([MOX₄]^?)_n strands. The structures of the cationic strands are closely related to the tellurium subhalides Te₂X (X = Br, I). One of the two rows of halogen atoms that bridges the band of condensed Te₆ rings is stripped off, and additionally one Te position has only 75% occupancy which leads to the formula ([Te₁₅X₄]²⁺)_n (X = Cl, Br) for the cation. The anionic substructures consist of tetrahalogenooxometalate ions [MOX₄]^? that are linked by linear oxygen bridges to polymeric strands. The compounds are paramagnetic with one unpaired electron per metal atom indicating oxidation state M^v, and are weak semiconductors.     

Das erste Bromid mit trigonal-bipyramidalen [M5(C2)]-Clustern: [Pr5(C2)]Br9

The First Bromide with Trigonal-Bipyramidal [M₅(C₂)] Clusters: [Pr₅(C₂)]Br₉ The bromide [Pr₅(C₂)]Br₉ is obtained via metallothermic reduction of PrBr₃ with rubidium in the presence of praseodymium and carbon in a sealed niobium container at 730°C as dark red single crystals. [Pr₅(C₂)]Br₉ crystallizes in the monoclinic crystal system [P2₁/n; Z = 4; a = 1 006.9(1); b = 1 886.1(1); c = 1 045.9(1) pm; β = 108.130(1)°; R_int = 0.059; R1 = 0.038; wR2 = 0.077]. One edge in the base of the trigonal bipyramid in [Pr₅(C₂)]Br₉ is usually long (440 pm). It is not brigded by a Brⁱ ligand. In addition to the eight Brⁱ, the cluster is coordinated by 12 terminal ligands (Br^a). Except for the known Br^a–a–a and Br^i–a connections, Br^i–a–a brigdes are observed for the first time for trigonal-bipyramidal clusters.     

Synthesis and Structural Characterization of New Phases in the Cubic M3Te2O6X2 (M = Sr,Ba; X = Cl,Br) Structure Family

Four alkaline earth oxotellurate(IV) halides with common formula M₃Te₂O₆X₂ (M = Sr, Ba; X = Cl, Br) have been prepared as polycrystalline powders and/or in the form of single crystals. All compounds crystallize in the cubic space group Fd$\bar{3}$ m with cell parameters a = 15.9351(4) Å for Sr₃Te₂O₆Cl₂ (single‐crystal X‐ray data), 16.052(5) Å for Sr₃Te₂O₆Br₂ (powder X‐ray data), 16.688(2) Å for Ba₃Te₂O₆Cl₂ (single‐crystal X‐ray data) and 16.8072(3) Å for Ba₃Te₂O₆Br_1.64Cl_0.36 (single‐crystal X‐ray data). The results of the crystal structure analyses reveal a rigid ${3}\atop{{\infty}}$ [M₃Te₂O₆]²⁺ framework which can be described as being composed of regular octahedra of two types of chemically non‐bonded M₆ octahedra that are capped by trigonal pyramidal [TeO₃] anions located above every second face of one of the M₆ octahedra. The halide X^– anions are situated in the voids of the ${3}\atop{{\infty}}$ [M₃Te₂O₆]²⁺ framework. Dependent on the nature of the halogen, the anions show various kinds of occupational disorder which eventually led to a revision of the previous structure model of Ba₃Te₂O₆Cl₂. A comparative discussion with other structures of general formula M₃Ch₂O₆X₂ (M = divalent metal; Ch = Te, Se; X = Cl, Br) is presented.     

Synthesis,Structure, and UV–Vis Characterization of Antimony(III) Phthalocyanine: [(SbPc)2(Sb2I8)(SbBr3)]2

A new antimony(III)–phthalocyanine complex with the formula of [(SbPc)₂(Sb₂I₈)(SbBr₃)]₂ has been obtained in the reaction of pure antimony powder with phthalonitrile under the oxidation conditions by iodine monobromide vapors. The complex crystallizes in the centrosymmetric space group of the triclinic system. Both independent (SbPc)⁺ units exhibit non-planar conformation, since the Sb(III) is larger than the equilibrium cavity size of the ring and cannot be accommodated without its expansion; thus, the metal protrudes out of the cavity, forming a saucer shape. The centrosymmetric anionic unit of the crystal consists of two (Sb₂I₈)²⁻ interacted anionic units forming (Sb₄I₁₆)⁴⁻ anionic complex that interacts with two SbBr₃ molecules to form [Sb₆I₁₆Br₆]⁴⁻ anionic aggregate. Each [Sb₆I₁₆Br₆]⁴⁻ anionic aggregate is surrounded by four (SbPc)⁺ cations forming a supramolecular centrosymmetric (SbPc)₄[Sb₆I₁₆Br₆] complex. Translationally related (SbPc)₄[Sb₆I₁₆Br₆] molecules form a stacking structure along the [100] and [011] directions with N₄–N₄ distances of 3.55 and 3.53 Å, respectively, between the back-to-back-oriented saucer-shaped (SbPc)⁺ units. The interaction between the building units of the crystal was analyzed using the Hirshfeld surface and the analysis of the 2D fingerprint plots. The UV–Vis absorption spectra of crystal 1 were taken in CH₂Cl₂ and toluene solutions in the concentration range from 10⁻⁵ to 10⁻⁶ mol/L. No significant changes related to aggregation in solutions were observed. The Q-band in toluene solution is red shifted by ~15 nm in comparison to that in CH₂Cl₂ solution. Oxidation of (SbPc)₄[Sb₆I₁₆Br₆] yields Sb^VPc derivative. Both Sb^III and Sb^V phthalocyanine derivatives absorb near infrared light (600–900 nm), which should be intriguing from the point of view of potential use as photosensitizers for PDT and as an infrared cut filter for plasma display and silicon photodiodes.     

Nb2Y2X6, a Novel Type of NbIV Compounds with Cross-linked Nb2 and Y2 Dumbbells (Y = Se,Te; X = Br,I)

The compounds Nb₂Se₂Br₆, Nb₂Te₂Br₆, and Nb₂Te₂I₆ were prepared from the elements in sealed quartz ampoulès at 1073 K. The crystalline solids, exhibiting a metallic lustre, are insensitive against moisture and oxygen. All compounds undergo several reversible thermal transitions with temperature (DTA). Beside binary halides only NbYX₃ is present in the gas phase. The structures consist of one-dimensional infinite chains of halogen bridged Nb₂(Y₂)X₄ units containing single side-on bonded Nb₂ and Y₂ dumbbells forming a quasi tetrahedral Nb₂Y₂ cluster (Nb? Nb ? 283.2; 287.5; 293.2 pm; Se? Se ? 230.5 pm; Te? Te ? 267.0; 268.5 pm). The structural and magnetic properties clearly prove the formal oxidation states Nb⁴⁺ and Y^1?, unexpected from stoichiometry. (Structural data: all P2/a (No. 13); Nb₂Se₂Br₆: a = 1254.0(12); b = 689.7(10); c = 662.4(10) pm; β = 98.9(1)°; Z = 2; 1274 hkl; R = 0.066. Nb₂Te₂Br₆: a = 1259.7(13); b = 713.5(9); c = 667.0(9) pm; β = 97.6(1)°; 1557 hkl; R = 0.043. Nb₂Te₂I₆: a = 1347.3(3); b = 742.9(2); c = 714.1(2) pm; β = 98.52(2)°; 1540 hkl; R = 0.026).     

An electrochemical investigation on the reduction path of the arene complexes [CpM(arene)]2+ and [(η-9-SMe2-7,8-C2B9H10)M(arene)]2+ (M=Rh, Ir)

The reduction behavior of the isoelectronic complexes [CpM^III(η⁶-C₆R₆)]²⁺ (M=Rh, Ir; R=H, Me) and [(η-9-SMe₂-7,8-C₂B₉H₁₀)M^III(η⁶-C₆R₆)]²⁺ (M=Rh, Ir; C₆R₆ = C₆H₆, C₆H₅OMe, C₆H₃Me₃) has been studied by cyclic voltammetry and controlled potential coulometry in acetonitrile and propylene carbonate at 253 and 298 K, respectively. The extent of chemical reversibility of the pertinent sequences Rh(III)/Rh(II)/Rh(I) and Ir(III)/Ir(I) is highly dependent on both the nature of the solvent and the intrinsic electronic properties of the arene substituents. The arene η⁶ coordination makes the derivatives in their lower oxidation states notably short lived, even if, in some cases, the use of propylene carbonate improves their stability or causes the increase in their lifetimes before changing the arene coordination from η⁶ to η⁴. Cations [(η-9-SMe₂-7,8-C₂B₉H₁₀)M(η⁶-C₆R₆)]²⁺ were obtained by the bromide abstraction from [(η-9-SMe₂-7,8-C₂B₉H₁₀)MBr₂]₂ with Ag⁺ in the presence of benzene and its derivatives. The structure of [(η-9-SMe₂-7,8-C₂B₉H₁₀)Ir(η⁶-C₆H₅OMe)](BF₄)₂ was determined by X-ray diffraction.     

The Photochemistry of the (Cycloalkene)(hydro)(trispyrazolylborato)iridium Complexes [Ir(η4-cod)(TpMe2)] and [Ir(η2-coe)H2(TpMe2)]: the Formation of [IrH4(TpMe2)] and [Ir(CO)H2(TpMe2)]

Photolysis of [Ir(η²-coe)H₂(Tp^Me2)] ( 1 ; Tp^Me2=hydrotris(3,5-dimethylpyrazolyl)borato, coe=(Z)-cyclooctene) in CH₃OH gives a mixture of [IrH₄(Tp^Me2)] ( 4 ) and [Ir(CO)H₂(Tp^Me2)] ( 5 ) in a ca. 1 : 1 ratio. Mass-spectral analysis of the distillate of the reaction mixture at the end of the photolysis shows the presence of coe. When pure CD₃OD is used as solvent, the deuteride complexes [IrD₄(Tp^Me2)] ((D₄)- 4 ) and [Ir(CO)D₂(Tp^Me2)] ((D₂)- 5 ) are obtained. Also the photolysis of [Ir(η⁴-cod)(Tp^Me2)] ( 3 ) (cod=cycloocta-1,5-diene) gives 4 and 5 . A key feature of this photoreaction is the intramolecular dehydrogenation of cod with formation of cycloocta-1,3,5-triene, detected by mass spectroscopy at the end of the photolysis. Labeling experiments using CD₃OD show that the hydrides in 4 originate from MeOH. When ¹³CH₃OH is used as solvent, [Ir(¹³CO)H₂(Tp^Me2)] is formed demonstrating that CH₃OH is the source of the CO ligand. The observation that the photolysis of both 1 and 3 give the same product mixture is attributed to the formation of a common intermediate, i.e., the coordinatively unsaturated 16e⁻ species {IrH₂(Tp^Me2)}.     

Reactivity of [Mo(NHNRPh)(NNRPh)(acac)X2] (R=Ph,Me; X=Br,I) toward tertiary phosphines

The reactivity of mixed [organohydrazido(1-)][organohydrazido(2-)]molybdenum(VI) complexes [Mo(NHNRPh)(NNRPh)(acac)X₂] {R?=?Ph, X?=?Br (1); R?=?Ph, X?=?I (2) and R?=?Me; X?=?I (3)} with tertiary phosphines as PPh₃, PMePh₂ and PMe₂Ph are examined. The syntheses of [Mo(NNPh₂)₂Br₂(PPh₃)] (4), [Mo(NNPh₂)₂Br₂(PMePh₂)₂] (5), [Mo(NNPh₂)₂Br₂(PMe₂Ph)₂] (6), [Mo(NNPh₂)₂(acac)I(PPh₃)] (7), [Mo(NNPh₂)₂(acac)(PMePh₂)₂]⁺I^? (8) and [Mo(NNMePh)₂(acac)(PMePh₂)₂]⁺I^? (9) are reported. All complexes were characterized by elemental analysis, UV-visible, IR, ¹H and ³¹P{H} NMR spectroscopy.     

Some transition metal complexes of new terdentate ligands: Bis[2-(diphenylphosphino)ethyl]benzylamine and bis[2-(diphenylarsino)ethyl)benzylamine

Complexes of the terdentate ligands bis[2-diphenylphosphino)ethyl]benzylamine (DPBA) and bis[2-(diphenylarsino)ethyl]benzylamine (DABA) with Co(II), Ni(II), Pd(II), Pt(II), Rh(III), Ir(III), Rh(I) and Ir(I) are reported. The ligand DPBA reacts with Co(II) ion to form two types of complexes: a high-spin, paramagnetic, tetrahedral Co(II) complex of composition [CoCl(DPBA)]Cl and a low-spin, paramagnetic, square-planar complex of composition [CoBr(DPBA)]B(C₆H₅)₄. The reaction of DPBA with Ni(II) ion in methanol yields low-spin, diamagnetic, square-planar complexes of type [NiX(DPBA)]Y [X = Cl, Br or I; Y = Cl or B(C₆H₅)₄]. Four-coordinate, square-planar, cationic complexes of type [MY(L⁺[M = Pd(II), Pt(II), Rh(I) or Ir(I); Y = Cl or P(C₆H₅)₃; L = DPBA or DABA], were obtained on reaction of L with various starting materials containing these metal ions. Reaction of DPBA and DABA with rhodium and iridium trichlorides gave octahedral, neutral complexes of general formula [MCl₃(L)] (M = Rh or Ir, L = DPBA or DABA). All the complexes were characterized on the basis of their elemental analysis, molarconductance data, magnetic susceptibilities, electronic spectra, IR spectral measurements, and¹H and³¹P-{¹H} NMR spectral data.     

Die Kristallstrukturen der Polytelluride [Ca(DMF)6]Te4, [Sr(15-Krone-5)2]Te4 · H2O, {[BaCl(18-Krone-6)(DMF)2]2[BaCl(18-Krone-6)(DMF) (H2O)]2(Te4)2} und [Ph3PNPPh3]2Te5 · 2 DMF

Crystal Structures of the Polytellurides [Ca(DMF)₆]Te₄, [Sr(15-Crown-5)₂]Te₄ · H₂O, {[BaCl(18-Crown-6)(DMF)₂]₂[BaCl(18-Crown-6)(DMF) (H₂O)]₂(Te₄)₂}, and [Ph₃PNPPh₃]₂Te₅ · 2 DMF The title compounds were formed by alkalimetal polytelluride solutions in dimethylformamide (DMF) in the presence of the corresponding counter ions as well as in the presence of 15-crown-5 or 18-crown-6. Single crystals were obtained upon using additional diethylether. [Ca(DMF)₆]Te₄: Space group C2/c, Z = 4, 1024 observed unique reflections, R = 0.055. Lattice dimensions at ?70°C: a = 1776.1; b = 813.0 c = 2545.9pm; β = 102.90°. The compound consists of centrosymmetric [Ca(DMF)⁶]²⁺ ions, in which the calcium ions are octahedrally coordinated by the six oxygen atoms of the DMF molecules, and chain-like Te [Sr)15-crown-5)₂]Te₄ · H₂O: Space group C2/c, Z = 4, 3322 observed unique reflections, R = 0.058. Lattice dimensions at ?70°C: a = 1450.5; b = 1407.3; c = 1660.9 pm; β = 110.22°. The compounds forms centrosymmetric cations [Sr(15-crown-5) ₂]²⁺, in which the Sr²⁺ ion is sandwich-like surrounded by the ten oxygen atoms of the crown ether molecules, and chain-like Te₄^2? ions, which are associated in the lattice forming polymeric chains. {[BaCl(18-crown-6)(DMF) ₂]₂[BaCl(18-crown-6)(DMF)· (H₂O)] ₂(Te₄)₂}: Space group P1 , Z = 1, 3189 observed unique reflections, R = 0.054. Lattice dimensions at 19°C: a = 986.1; b = 1052.8; c = 2696.4 pm; α = 89.34°; β = 88.68°; γ = 89.56°. The compound consists of chain-like Te ions without symmetry and of the two somewhat different cations [BaCl(18-crown-6)(DMF) ₂]₂²⁺, in which the Ba²⁺ ions dimerize via centroysmmetric rings. Along with the six oxygen atoms of the crown ether molecules and the oxygen atoms of the DMF molecules, the oxygen atoms of the DMF and water molecule, respectively, the Ba⁺ ions achieve coordination number ten. [Ph₃PNPPh₃]₂Te₅ · 2DMF: Space group Pc, Z = 2, 5971 observed unique reflections, R = 0.058. Lattice dimensions at 20°C: a = 20°C: a = 1085.2; b = 1287.0; c = 2715.9 pm; β = 90.19°. The compounds consists of [Ph₃PNPPh₃]₊ ions, chain-like Te₅^2? ions, and incorporate DME molecules without bonding interaction. The ₅^2? ions are associate via polymeric chains in which left- and right handed individuals are alternating.     

Solvothermal Synthesis and Crystal Structure of Te8[U2Br10], Containing a Polymeric Chalcogen Cation (Te82+)n

Under solvothermal conditions, the reaction of Te, TeBr₄ and UBr₅ in SiBr₄ at 200?C yields Te₈[U₂Br₁₀] as silvery crystals. The crystal structure (triclinic, P&1macr;, a = 900.8(4), b = 1205.1(5), c = 1366.0(6) pm, α = 80.93(4)?, β = 76.83(3)?, γ = 78.84(3)?, Z = 2) is built of one‐dimensional polymeric (Te₈²⁺)_n cations consisting of boat‐shaped Te₆ rings, which are linked by Te₂ bridges. The anions [U₂Br₁₀^2‐]_n are also polymeric, consisting of edge sharing UBr₇ pentagonal bipyramids [UBr₃Br_4/2^2‐]_n and contain U(IV). Both chains are parallel to each other and run along the crystallographic a‐axis. The cation represents a formerly unknown isomer of Te₈²⁺ ions. So far, Te₈²⁺ has been known as molecular clusters in Te₈[MCl₆](M = Zr, Hf, Re) and (Te₈)(Te₆)[WCl₆]₄, or in form of linked bicyclic monomers that are present in Te₈[WCl₆]₂. A polymeric chain‐like form closely related to Te₈[U₂Br₁₀] was found in Te₈[Bi₄Cl₁₄].     

Cubane Tellurido Clusters [Zn(NH3)4]3[Mo4Te4(CN)12] and [Cd(NH3)4]3[W4Te4(CN)12]: Syntheses and Crystal Structures

Single crystals of [Zn(NH₃)₄]₃[Mo₄Te₄(CN)₁₂] (I) and [Cd(NH₃)₄]₃[W₄Te₄(CN)₁₂] (II) were obtained by applying solutions of K₇[Mo₄Te₄(CN)₁₂] · 11H₂O and K₆[W₄Te₄(CN)₁₂] · 5H₂O in aqueous ammonia over solutions of ZnCl₂ and Cd(NO₃)₂ in glycerol and were characterized by X-ray diffraction analysis. The IR spectra and thermal properties of compounds I and II were examined.     

Syntheses of [Rh(NH3)5Cl][MCl6] (M = Re, Os, Ir) and Investigation of Their Thermolysis Products. Crystal Structure of [Rh(NH3)5Cl][OsCl6]

Binary complex salts [Rh(NH₃)₅Cl][MCl₆], where M = Re, Os, Ir, have been synthesized and characterized. X-ray diffraction analysis indicated that the salts are isostructural. According to X-ray phase analysis, the products of their thermolysis in hydrogen are monophase stoichiometric nonequilibrium solid solutions Rh_0.5M_0.5 (M = Re, Os, Ir). The molecular and crystal structures of [Rh(NH₃)₅Cl][OsCl₆] were determined in an X-ray structural analysis.