Basische metalle : XX. Synthese und reaktivität von C6Me6Ru(CO)PMe3. Ein stabiler aromaten-ruthenium(0)-carbonyl-komplex

Treatment of [C₆Me₆RuCl₂]₂ with carbon monoxide gives C₆Me₆Ru(CO)Cl₂ (II) which reacts with PMe₃ in the presence of NH₄PF₆ to form [C₆Me₆Ru(CO)(PMe₃)Cl]PF₆ (III). Reduction of the cation of III with NaC₁₀H₈ in THF yields C₆Me₆Ru(CO)PMe₃ (IV) which is the first stable mononuclear areneruthenium(0) carbonyl complex. IV reacts with CF₃COOH/NH₄PF₆ and MeI/NH₄PF₆ to give the stable salts [C₆Me₆RuH(CO)PMe₃]PF₄ (V) and [C₆Me₆RuCH₃(CO)PMe₃]PF₆ (VI).     

Basische metalle : IX. Synthese und kristallstruktur von C5H5Co(PMe3)CS2. Reaktionen zu zweikernkomplexen mit Co(SCS)Cr- und Co(SCS)Mn-Brückenbindungen

C₅H₅Co(PMe₃)CS₂ (IV) is formed in practically quantitative yield in the reaction of C₅H₅Co(PMe₃)₂ (I) or the heterobinuclear complex C₅H₅(PMe₃)Co(CO)₂Mn(CO)C₅H₄Me (III) with CS₂. The crystal structure shows that the carbon disulfide bonds as a dihapto ligand through the carbon and one sulfur atom (S(2)) (CoC = 1.89, CoS(2) = 2.24 Å, S(2)CS(1) = 141.2°). The two CS bond lengths in IV (CS(2) = 1.68, CS(1) =1.60 Å) are greater than in free CS₂ (1.554Å) which is in agreement with the strong π-acceptor character of h²-CS₂ as shown in the spectroscopic data. IV reacts with Cr(CO)₅THF and C₅H₅Mn(CO)₂THF to give the complexes C₅H₅(PMe₃)Co(SCS)Cr(CO)₅ (V) and C₅H₅(PMe₃)Co(SCS)Mn(CO)₂C₅H₅ (VI) respectively, in which the sulfur atom S(1) that is not bound to cobalt coordinates to the 16-electron fragments Cr(CO)₅ and Mn(CO)₂C₅H₅. The spectroscopic data of IV, V and VI are discussed.     

Basische Metalle. XIII. Ein neuer Syntheseweg für Cyclopentadienyl-Rhodium-Phosphonat- aus Cyclopentadienyl-Rhodium-Phosphit-Komplexen

Basic Metals. XIII. A New Synthesis of Cyclopentadienylrhodium Phosphonate from Cyclopentadienylrhodium Phosphite Complexes C₅H₅Rh[P(OCH₃)₃]₂ reacts with alkali metal iodides MI (M = Li, Na, K) in two stages via the intermediate C₅H₅RhCH₃[P(O)(OCH₃) ₂]P(OCH₃)₃ to the corresponding bisphosphonate complexes C₅H₅RhCH₃[P(O)(OCH₃) ₂]₂M. Their properties suggest that they exist as contact ionpairs rather than dissociated ions. The reaction of C₅H₅RhCH₃[P(O)(OCH₃)₂]₂ Na with HCl in benzene yields the complex C₅H₅RhCH₃[P(O)(OCH₃) ₂]₂H, in which a chelate ligand with a P? O? H? O? P bridge is probably present. The acidic character of the bridging H atom is shown in the reaction with (CH₃)₃PCH₂ which leads to [C₅H₅RhCH₃{P(O)(OCH₃) ₂}₂][P(CH₃)₄]. C₅H₅RhCH₃[P(O)(OCH₃) ₂]₂Tl was formed in the reaction of C₅H₅RhCH₃[P(O)(OCH₃)₂]₂ H and thallium acetylacetonate. The n.m.r. spectra of the new phosphonate complexes are discussed.     

Synthese und Kristallstruktur von Rb3PbCl5

Synthesis and Crystal Structure of Rb₃PbCl₅ The synthesis of the hitherto unknown compound Rb₃PbCl₅ in the quasi-binary system RbCl/PbCl₂ and its structure determination is reported. This 3 : 1-phase decomposes peritectoidally at 305 °C and crystallizes in a so far unknown structure type in the orthorhombic space group Pnma (a = 863.498(5) pm, b = 1573.11(1) pm, c = 838.875(5) pm). It shows typical structural characteristics of ns²-configurated cations, although there are more noble gas-configurated cations than ns²-configurated cations in the structure.     

Basische metalle : XXXVI. Die synthese stabiler hydrido(olefin)rhodium-komplexe und von[C5H5Rh(PMe3)(η3-CH3CHC6H5)]PF6

The complexes C₅H₅Rh(PMe₃)C₂H₃R′ (R′  H, Me, Ph) and C₅H₅Rh(PR₃)C₂H₄(PR₃  PMe₂Ph, PPrⁱ₃) are prepared by reaction of[PMe₃(C₂H₃R/t')RhCl]₂ or [PR₃(C₂H₄)RhCl]₂ and TlC₅H₅, respectively. They react with HBF₄ in ether/propionic anhydride to form the BF₄ salts of the hydrido(olefin)rhodium cations [C₅H₅RhH(C₂H₃R′)PR₃]⁺(R  Me; R′  H, Me and R  Prⁱ; R′  H). From C₅H₅Rh(PMe₃)C₂H₃Ph and CF₃COOH/NH₄PF₆ the η³-benzyl complex [C₅H₅Rh(PMe₃)(η³-CH₃CHC₆H₅)]PF₆ is obtained. The reversibility of the protonation reactions is demonstrated by temperature-dependent NMR spectra and by deuteration experiments. The complexes C₅H₅Rh(PMe₃)C₂H₃R′ (R′  H, Ph) and C₅H₅Rh(PMe₂Ph)C₂H₄ react with CH₃I in ether to give the salts [C₅H₅RhCH₃(C₂H₃R′)PR₃]I which in THF or CH₃NO₂ yield the neutral compounds C₅H₅RhCH₃(PR₃)I.     

Synthese und Kristallstruktur von (C5H5)Mo(CO)3(AuPPh3) und [(C5H5)Mo(CO)2(AuPPh3)4]PF6

Synthesis and Crystal Structure of (C₅H₅)Mo(CO)₃(AuPPh₃) and [(C₅H₅)Mo(CO)₂(AuPPh₃)₄]PF₆ CpMo(CO)₃(AuPPh₃) is obtained by the reaction of Li[CpMo(CO)₃] with Ph₃PAuCl at ?95°C in CH₂Cl₂. It crystallizes in the monoclinic space group C2/c with a = 2625.1(7), b = 883.2(1), c = 2328.4(7) pm, β = 116.39(1)° und Z = 8. In the complex the AuPPh₃ group is coordinated to the CpMo(CO)₃ fragment with a Au? Mo bond of 271,0 pm. The Mo atom thus achieves a square pyramidal coordination with the center of the Cp ring in apical position. CpMo(CO)₃(AuPPh₃) reacts under uv irradiation with an excess of Ph₃PAuN₃ to afford the cluster cation [CpMo(CO)₂(AuPPh₃)₄]⁺. It crystallizes as [CpMo(CO)₂(AuPPh₃)₄]PF₆ · 2 CH₂Cl₂ in the orthorhombic space group P2₁2₁2₁ with a = 1553.9(1), b = 1793.8(2), c = 2809.8(7) pm und Z = 4. The five metal atoms form a trigonal bipyramidal cluster skeleton with the Mo atom in equatorial position. The Mo? Au distances range from 275.5 to 280.8 pm, and the Au? Au distances are between 281.2 and 285.6 pm.     

Synthese und Kristallstruktur von CaBiVO5

Synthesis and Crystal Structure of CaBiVO₅ Single crystals of the hitherto unknown compound CaBiVO₅ were prepared and investigated by X-ray work. It crystallizes with orthorhombic symmetry, space group D? Pbca, a = 11.2022, b = 5.4283, c = 15.5605 Å, Z = 8. The crystal structure is characterized by layers of the edge-linked CaO₇ polyhedra, isolated VO₄ tetrahedra and an asymmetric surrounding of Bi³⁺ by oxygen.     

AgCo3H2(AsO4)3 und AgZn3H2(AsO4)3 Darstellung und Kristallstruktur Ein weiterer neuer Arsenat-Strukturtyp

AgCo₃H₂(AsO₄)₃ and AgZn₃H₂(AsO₄)₃. Preparation and Crystal Structure. Another New Structure Type of an Arsenate AgCo₃H₂(AsO₄)₃ ( 1 ) and AgZn₃H₂(AsO₄)₃ ( 2 ) were prepared by heating of As₂O₅, AgNO₃, CoSO₄ · 7H₂O, ZnSO₄ · 7H₂O, respectively, and water in a sealed tube at 300°C and investigated with X-rays. Both compounds are isotypic and crystallize in the monoclinic space group C2/c with 4 formula units per cell. The lattice parameters are ( 1 ): a = 1215.9(6), b = 1243.8(7), c = 678.2(3) pm, β = 113.16(3)° ( 2 ): a = 1216.9(2), b = 1249.5(3), c = 675.5(1) pm, β = 112.77(1)°. The structure contains chains of edge-shared CoO₆ or ZnO₆ octahedra, respectively, which are connected by AsO₄ tetrahedra and silver oxygen ribbons with square planar coordinated silver forming a framework. Based on the charge balances derived from the geometrical data and the IR spectra the occurence of hydrogen bonds is discussed.     

Synthese und Kristallstruktur von KTeOF3

Synthesis and Crystal Structure of KTeOF₃ KTeOF₃ has been synthesized by solid state reaction of KF, TeO₂ and KTeF₅ in equimolar amounts. Its crystal structure has been solved by single crystal structure analysis (P4₂/n, a = 1007.96(3), c = 789.58(3) pm, Z = 8, R₁ = 0.0311). As a characteristic feature, the compound contains unprecedented dimeric anions Te₂O₂F₆^2– formed by two edge‐sharing pseudo‐octahedral units. IR and Raman data are given.     

Synthese,Kristallstruktur und Festkörper-NMR-spektroskopische Untersuchungen von K5H(CN2)3

Synthesis, Crystal Structure, and Solid State MAS-NMR Spectroscopic Investigation of K₅H(CN₂)₃ Single phase K₅H(CN₂)₃ was synthesized by reaction of KHCN₂ with metallic potassium in liquid ammonia or by reaction of KNH₂ with melamine C₃N₃(NH₂)₃ at 320 °C, respectively. The crystal structure was determined from X-ray powder and single crystal data: K₅H(CN)₃, space group Im3m, a = 795.68(7) pm, Z = 2, R1 = 0.025, wR2 = 0.0438. In the solid K₅H(CN₂)₃ contains K⁺ and CN₂^2–, the anions exhibit D_∞h symmetry. According to ¹H and ¹³C solid state MAS-NMR investigations, temperature dependent impedance spectroscopy, and FTIR spectroscopy the protons are only loosely bound to the CN₂^2– ions. The proton conductivity shows a sharp increase above 70 °C.     

Über die Kristallstruktur von (C6H5)3SiSH und (C6H5)3SiSBr und die Darstellung des Iodsulfans (C6H5)3SiSI

The Crystal Structure of (C₆H₅)₃SiSH and (C₆H₅)₃SiSBr and the Preparation of the Iodosulfane (C₆H₅)₃SiSI The preparation of the halogenosulfanes Ph₃SiSBr and Ph₃SiSI from Ph₃SiSH and N-halogenosuccinimide is reported. They are characterized by vibrational spectroscopic measurements. Ph₃SiSBr crystallizes in space group P1 with a = 899.3(8) pm, b = 941.3(7) pm, c = 1 051.4(7) pm, α = 109.88(5)°, β = 99.23(6)°, γ = 96.78(6)° and Z = 2. Ph₃SiSH crystallizes in space group P2₁/c with a = 1 879.4(8), b = 966.3(5), c = 1 845.2(9), β = 107.84(4), Z = 8. The halogenosulfanes decompose in polar solvents by formation of sulphur and triphenylsilanhalide.     

Synthese,Kristallstruktur und Schwingungsspektren von Dimethylphosphoniumtetrachloroaluminat,H2PMe2+AlCl4–

Synthesis, Crystal Structure, and Vibrational Spectra of Dimethylphosphonium Tetrachloroaluminate, H₂PMe₂⁺AlCl₄^– H₂PMe₂⁺AlCl₄^– was synthesized by the reaction of Me₂PH with HCl and AlCl₃ in CH₂Cl₂. The structure of the compound was determined by X‐ray structure determination. H₂PMe₂⁺AlCl₄^– crystallizes in the monoclinic space group P2₁/c with a = 14.445(1), b = 11.344(1) and c = 12.394(1) Å, β = 90.00(1)°, with 8 formula units per unit cell. The frequencies obtained by Raman and infrared spectroscopy were assigned to the normal modes of the H₂PMe₂⁺ and AlCl₄^– units.     

Synthese und Kristallstruktur von Bis(1,2-dimethyl-5-nitro-imidazol)dichlorocobalt(II)

Synthesis and Crystal Structure of Bis(1,2-dimetyl-5-nitro-imidazole)dichlorocobalt(II) Bis(1,2-dimethyl-5-nitro-imidazol)dichlorocobalt(II) was obtained by reaction of CoCl₂ · 6 H₂O with 1,2-dimethyl-5-nitro-imidazole in methanol. The compound forms blue crystals which were characterized by IR and UV-vis spectroscopy and by an X-ray crystal structure determination. Co(C₅H₇N₃O₂)₂Cl₂: tetragonal, space group I4 2d, Z = 8, a = 1142.1(1) pm, c = 2577.3(2) pm. R = 0.036 for 670 independent reflexions. The Co atom is tetrahedrally surrounded by two chlorine and two N atoms at distances of 222.8(2) and 203.5(4) pm.     

Synthese und Kristallstruktur von Praseodympropionat-trihydrat,Pr(CH3CH2COO)3(H2O)3

Synthesis and Crystal Structure of Praseodymium Propionate Trihydrate, Pr(CH₃CH₂COO)₃(H₂O)₃ Single crystals of Pr(CH₃CH₂COO)₃(H₂O)₃ were obtained by dissolving freshly prepared praseodymium hydroxide in diluted propionic acid. The crystal structure (monoclinic, P2₁/c, Z = 4, a = 1034.2(2) pm, b = 1521.2(3) pm, c = 2086.3(7) pm, β = 102.87(2)°, R1 = 0.0864, wR2 = 0.1196) consists of one-dimensional infinite chains parallel [010]. Pr1 and Pr2 are coordinated by four tridentate-bridging propionate groups. Additionally, Pr1 is coordinated by three “coordination water” molecules, Pr2 by two bidentate propionate groups. There are, in addition, three “crystal water” molecules so that praseodymium propionate trihydrate should be formulated as [(H₂O)₃Pr1(CH₃CH₂COO)₄Pr2(CH₃CH₂COO)₂] (H₂O)₃.     

Ein Polyphosphid mit Rhenium-Clustern: Synthese und Kristallstruktur von Re6P13

A Polyphosphide with Rhenium Clusters: Synthesis and Crystal Structure of Re₆P₁₃ Microcrystalline Re₆P₁₃ was prepared by heating the elemental components in the presence of iodine. Single crystals were obtained by reaction of the components in molten tin. They are rhombohedral, R3 , with the hexagonal cell dimensions: a = 15.665(9), c= 8.320(2) Å, Z = 6. The structure was determined and refined from single-crystal data(R = 0.053). The Re atoms are coordinated by six P atoms in distorted octahedral configuration. Four edge-sharing octahedra are distorted in such a way that Re? Re bonds (2.76 to 2.94 Å) are formed. All P atoms are tetrahedrally coordinated by Re and P atoms. The P atoms form six-membered rings, four membered chains, and pairs. One P atom has only Re neighbors. The crystal structure of Re₆P₁₃ is discussed together with the structures of related compounds.