Darstellung und Kristallstrukturen von [P(C6H5)4][1-(NH3)B10H9] und Cs[(NH3)B12H11] · 2CH3OH

Synthesis and Crystal Structures of [P(C₆H₅)₄][1-(NH₃)B₁₀H₉] and Cs[(NH₃)B₁₂H₁₁] · 2CH₃OH The reduction of [1-(NO₂)B₁₀H₉]^2? with aluminum in alkaline solution yields [1-(NH₃)B₁₀H₉]^? and by treatment of [B₁₂H₁₂]^2? with hydroxylamine-O-sulfonic acid [(NH₃)B₁₂H₁₁]^? is formed. The crystal structures of [P(C₆H₅)₄][1-(NH₃)B₁₀H₉] (triclinic, space group P1 , a = 7.491(2), b = 13.341(2), c = 14.235(1) Å, α = 68.127(9), β = 81.85(2), γ = 86.860(3)°, Z = 2) and Cs[(NH₃)B₁₂H₁₁] · 2CH₃OH (monoclinic, space group P2₁/n, a = 14.570(2), b = 7.796(1), c = 15.076(2) Å, β = 111.801(8)°, Z = 4) reveal for both compounds the bonding of an ammine substituent to the cluster anion.     

Synthese und Struktur von [(Ph3C6H2)Te]2, [(Ph3C6H2)Te(AuPPh3)2]PF6 und [(Ph3C6H2)TeAuI2]2

Synthesis and Structure of [(Ph₃C₆H₂)Te]₂, [(Ph₃C₆H₂)Te(AuPPh₃)₂]PF₆ and [(Ph₃C₆H₂)TeAuI₂]₂ [(2,4,6-Ph₃C₆H₂)Te]₂ reacts with Ph₃PAu⁺ to yield [2,4,6-Ph₃C₆H₂TeAuPPh₃₂]PF₆ which can be oxidized by I₂ to form the gold(III) complex [(2,4,6-Ph₃C₆H₂)TeAuI₂]₂. [(2,4,6-Ph₃C₆H₂)Te]₂ crystallizes in the monoclinic space group P2₁/c with a = 810.6(2); b = 2026.5(5); c = 2260.6(7) pm; β = 99.23(3)° and Z = 4. In the crystal structure the ditelluride exhibits a dihedral angle C11? Te1? Te2? C21 of 66.1(2)°. The distance Te1? Te2 is 269.45(6) pm. In the cation of the triclinic complex [(2,4,6-Ph₃C₆H₂)Te(AuPPh₃)₂]PF₆ (space group P1 ; a = 1197.4(3); b = 1457.2(4); c = 1680.0(6) pm; α = 84.69(3)°; β = 85.11(3)°; γ = 75.54(3)°; Z = 2) a pyramidal skeleton RTeAu₂ with distances Te? Au = 259.2(1) and 257.8(2) pm and Au? Au = 295.3(1) pm is present. [(2,4,6-Ph₃C₆H₂)TeAuI₂]₂ crystallizes in the triclinic space group P1 with a = 1086.3(3); b = 1462.9(6); c = 1654.2(2) pm; α = 85.25(2)°; β = 87.44(1)°; γ = 80.90(3)°; Z = 2. In the centrosymmetrical dinuclear complex [(2,4,6-Ph₃C₆H₂)TeAuI₂]₂ the Au atoms exhibit a square-planar coordination by two iodine atoms and two tellurolate ligands. The tellurolate ligands form symmetrical bridges with distances Te? Au = 260.0 pm. The distances Au? I are in the range of 260.3(1) and 263.7(1) pm.     

Replacement of Trimethylamine in Trimethylamine‐trispentafluoroethyl‐borane. Structures of [(C2F5)3BNMe3], [NMe4][(C2F5)3BOH], and K[(C2F5)3BCH2(CO)C6H5]

Trimethylamine‐tris(pentafluoroethyl)borane [(C₂F₅)₃BNMe₃] ( 1 ) reacts at 190 °C with water under displacement of the trimethylamine ligand to yield the hydroxy‐tris(pentafluoroethyl)borate [(C₂F₅)₃BOH]^? ( 2 ). In tributylamine 1 reacts with alkynes HC≡CR to form novel ethynyl‐tris(pentafluoroethyl)borate anions [(C₂F₅)₃BC≡CR]^? – R = C₆H₅ ( 3 ), C₆H₄CH₃ ( 4 ), Si(CH(CH₃)₂)₃ ( 5 ) – in moderate yields. Compound 3 adds water across the triple bond to form the novel anion [(C₂F₅)₃BCH₂(CO)C₆H₅]^? ( 6 ). The structures of [(C₂F₅)₃BNMe₃], [NMe₄][(C₂F₅)₃BOH] and K[(C₂F₅)₃BCH₂(CO)C₆H₅] have been determined by x‐ray crystallography.     

Synthese und Kristallstrukturen von NH4[Si(NH3)F5] und [Si(NH3)2F4]

Synthesis and Crystal Structures of NH₄[Si(NH₃)F₅] and [Si(NH₃)₂F₄] Single crystals of NH₄[Si(NH₃)F₅] and [Si(NH₃)₂F₄] are obtained by reaction of silicon powder with NH₄HF₂ in sealed Monel ampoules at 400°C. NH₄[Si(NH₃)F₅] crystallizes with the tetragonal space group P4/n (no. 85) with a = 614.91(7) pm, c = 721.01(8) pm, Z = 2. Characteristic for the structure is the anionic octahedron [Si(NH₃)F₅]^?. Si(NH₃)₂F₄ crystallizes with the monoclinic space group P2₁/c (no. 14) with a = 506.9(1) pm, b = 728.0(1) pm, c = 675.9(1), β = 93,21(2)°, Z = 2. Trans-[Si(NH₃)₂F₄] molecules are characteristic for this structure.     

Synthese,Struktur und Eigenschaften von [(C4H9)2NH2]4[Sn2Se6], [(C4H9)2NH2]4[Sn4Se10] · 2 H2O und [(C3H7)3NH]2[Sn3Se7]

About Selenidostannates. I Synthesis, Structure, and Properties of [Sn₂Se₆]^4–, [Sn₄Se₁₀]^4–, and [Sn₃Se₇]^2– The selenidostannates [(C₄H₉)₂NH₂]₄Sn₂Se₆ · H₂O ( I ), [(C₄H₉)₂NH₂]₄Sn₄Se₁₀ · 2 H₂O ( II ) und [(C₃H₇)₃NH]₂Sn₃Se₇ ( III ) were prepared by hydrothermal syntheses from the elements and the amines. I crystallizes in the monoclinic spacegroup P2₁/n (a = 1262.9(3) pm, b = 1851.3(4) pm, c = 2305.2(4) pm, β = 104.13(3)° and Z = 4). The [Sn₂Se₆]^4– anion consists of two edge‐sharing tetrahedra. II crystallizes in the orthorhombic spacegroup Pna2₁ (a = 2080.3(4) pm, b = 1308.2(3) pm, c = 2263.5(5) pm and Z = 4). The anion is formed from four SnSe₄ tetrahedra which are joined by common corners to the adamantane cage [Sn₄Se₁₀]^4–. III crystallizes in the orthorhombic spacegroup Pbcn (a = 1371.1(3) pm, b = 2285.4(5) pm, c = 2194.7(4) pm and Z = 8). The anion is a chain, built from edge‐sharing [Sn₃Se₅Se_4/2]^2– units, in which two corner sharing tetrahedra are connected to a trigonal bipyramid by an edge of one and a corner of the other tetrahedron. The results of the TG/DSC measurements and of temperature dependent X‐ray diffractograms reveal that I and II decompose at first by release of minor quantities of triethylammonium to compounds with layer structure and larger cell dimensions. At still higher temperature the rest of triethylammonium and H₂Se is evolved, leaving SnSe₂ and Se in the bulk. The former decomposes partially at the highest temperature to SnSe. In the measurements of III the complex intermediate compound was not observed. III decomposes directly to SnSe₂.     

Electronic structure and spectra of [Ru(NH3)5pyz]2+ and [(NH3)5Ru-pyz-Ru(NH3)5]4+

The electronic structure and spectra of [Ru(NH₃)₅pyz]²⁺ and [(NH₃)₅Ru-pyz-Ru(NH₃)₅]⁴⁺ are calculated by the INDO (CINDO-E/S) method. Changes in molecular orbitals, charge distributions, and bond order indices of the pyrazine molecule and [Ru(NH₃)₅pyz]²⁺ complex in the [(NH₃)₅Ru-pyz-Ru(NH₃)₅]⁴⁺ binuclear complex are analyzed. St. Petersburg State University. Translated fromZhurnal Strukturnoi Khimii, Vol. 35, No. 4, pp. 12–23, July–August, 1994. Translated by. O. Kharlamova     

[(C2H5)3NH]2Sn3Se7 · 0,25 H2O und [(C3H7)2NH2]4Sn4Se10 · 4 H2O

Synthesis, Structure, and Properties of Some Selenidostannates. II. [(C₂H₅)₃NH]₂Sn₃Se₇ · 0,25 H₂O and [(C₃H₇)₂NH₂]₄Sn₄Se₁₀ · 4 H₂O The new selenidostannate hydrates [(C₂H₅)₃NH]₂Sn₃Se₇ · 0.25 H₂O ( I ) and [(C₃H₇)₂NH₂]₄Sn₄Se₁₀ · 4 H₂O ( II ) were synthesized from an aqueous suspension of triethylammonium (tripropylammonium), tin, selenium I and in addition sulfur II at 130 °C. I crystallizes at ambient temperature in the monoclinic space group P2₁/n (a = 2069,3(4) pm, b = 1396,6(3) pm, c = 2342,8(5) pm, β = 114,68(3)°, Z = 8) and is characterized by two different anions, chains from edge‐sharing [Se₃Se₇]^2– units and nets from trigonal SnSe₅ bipyramids. II crystallizes at ambient temperature in the tetragonal space group I4₁/amd (a = 2150,0(3) pm, c = 1174,4(2) pm, Z = 4) and contains adamantane like [Sn₄Se₁₀]^4–‐cages. The UV‐VIS spectra of the selenidostannates demonstrate that the absorption edges red shift as the dimensionality of the compounds is increased.     

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.     

Addition des O'Donnell Reagenzes [Ph2C=NCHCO2Me]– an π-koordinierte,ungesättigte Kohlenwasserstoffe in [(C6H7)Fe(CO)3]+, [(C7H9)Fe(CO)3]+, [(C7H7)M(CO)3]+ (M = Cr,Mo) und [(C2H4)Re(CO)5]+. α-Aminosäuren mit metallorganischen Seitenketten

Metal Complexes of Biologically Important Ligands. CXVII [1] Addition of the O'Donnell Reagent [Ph₂C=NCHCO₂Me]^– to Coordinated, Unsaturated Hydrocarbons of [(C₆H₇)Fe(CO)₃]⁺, [C₇H₉Fe(CO)₃]⁺, [(C₇H₇)M(CO)₃]⁺ (M = Cr, Mo), and [(C₂H₄)Re(CO)₅]⁺. α-Amino Acids with Organometallic Side Chains The addition of [Ph₂C=NCHCO₂Me]^– to [(C₆H₇)Fe(CO)₃]⁺, [(C₇H₉)Fe(CO)₃]⁺, [(C₇H₇)M(CO)₃]⁺ (M = Cr, Mo) and [(C₂H₄)Re(CO)₅]⁺ gives derivatives of α-amino acids with organometallic side chains. The structure of [(η⁴-C₆H₇)CH(N=CPh₂)CO₂Me]Fe(CO)₃ was determined by X-ray diffraction. From the adduct of [Ph₂C=NCHCO₂Me]^– and [(C₇H₇)Mo(CO)₃]⁺ the Schiff base of a new unnatural α-amino acid, Ph₂C=NCH(C₇H₇)CO₂Me, was obtained.     

Kristallstrukturen der Fluorochloroplatinate(IV) cis-[(C5H5N)2CH2][PtF4Cl2], trans-[(C5H5N)2CH2][PtF4Cl2] · H2O und [(C5H5N)2CH2][PtF5Cl]

Crystal Structures of the Fluorochloroplatinates(IV) cis-[(C₅H₅N)₂CH₂][PtF₄Cl₂], trans-[(C₅H₅N)₂CH₂][PtF₄Cl₂] · H₂O, and [(C₅H₅N)₂CH₂][PtF₅Cl] The complex ions cis-[PtF₄Cl₂]^2?, trans-[PtF₄Cl₂]^2? and [PtF₅Cl]^2? have been synthesized by stereoselective ligand exchange reactions utilizing the trans effect and are separated by ion exchange chromatography on diethylaminoethyl cellulose. These anions form stable AB-type salts with the doubly charged cation dipyridiniomethane, [(C₅H₅N)₂CH₂]²⁺. X-ray structure determinations on single crystals of cis-[(C₅H₅N)₂CH₂][PtF₄Cl₂] ( 1 ) (monoclinic, space group P2₁/n with a = 10.379(10), b = 9.635(2), c = 13.738(2) Å, β = 99.142(10)°, Z = 4), trans-[(C₅H₅N)₂CH₂][PtF₄Cl₂] · H₂O ( 2 ) (triclinic, space group P1 with a = 7.757(4), b = 10.059(7), c = 10.408(6) Å, α = 82.49(5), β = 68.92(4), γ = 75.46(4)°, Z = 2) and [(C₅H₅N)₂CH₂][PtF₅Cl] ( 3 ) (orthorhombic, space group Pnma with a = 10.394(3), b = 13.320(2), c = 9.2694(10) Å, Z = 4), reveal the perfect ordering of the anion sublattice. The stronger trans influence of Cl compared with F is observed in asymmetric axes $ {\rm F}^ \bullet $? Pt? Cl′. The bond lengths Pt? $ {\rm F}^ \bullet $ are 0.026 Å (1.4%) longer and the Pt? Cl′ distances are 0.078 Å (3,3%) shorter in comparison with those of symmetrically coordinated axes. The weakening of the Pt? $ {\rm F}^ \bullet $ bond and the strengthening of the Pt? Cl′ bond is better recognizable from shifts of the stretching vibrations by 8% to lower and by 13% to higher frequencies, respectively. Correspondingly, the valence force constants are found to be 15% lower and 22% higher. The trans influence is observed most distinctly in the ¹⁹F-nmr spectra exhibiting the coupling constant ¹J($ {\rm F}^ \bullet $Pt) to be 29% smaller than ¹J(FPt).     

Spektroskopische Untersuchungen an Eisen(II)-nitrosodicyan-methanid- und -nitrosocarbamoylcyanmethanid-Komplexen [Fe(NOC(CN)2)2(C5H5N)4] und [Fe(NOC(CN)C(O)NH2)2(C5H5N)2]

Spectroscopic Investigations of the Iron(II) Nitrosodicyanomethanide and Nitrosocarbamoylcyanomethanide Complexes [Fe(NOC(CN)₂)₂(C₅H₅N)₄] and [Fe(NOC(CN)C(O)NH₂)₂(C₅H₅N)₂] The syntheses of new iron(II) complexes of the nonlinear pseudohalides [NOC(CN)₂]^? and [NOC(CN)C(O)NH₂]^? is reported. The Structures of the compounds are discussed on the basis of IR, Mößbauer, ¹³C, and ¹⁴N NMR spectra as well as of the results of magnetic measurements.     

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).     

Zur Reaktion von Makrozyklen mit Lanthanoiden. II. Die Strukturen von [K(thf)3]2[(C22H28N4)2Sm2] · 4THF und [(C22H22N4)Co] · DME

On the Reaction of Macrocycles with Lanthanoids. II. The Crystal Structures of [K(thf)₃]₂[(C₂₂H₂₈N₄)₂Sm₂] · 4 THF and [(C₂₂H₂₂N₄)Co] · DME In a complicated redox reaction [(TMTAA)K₂] and [SmI₂(thf)₂] form the polynuclear metal complex [K(thf)₃]₂[(TMTAT)₂Sm₂]. This complex crystallizes with four molecules THF per formula unit and its structure was determined by single crystal X-ray investigation (spacegroup P2₁/c (No. 14), z = 4, a = 998.0(2) pm, = b = 2618.3(6) pm, c = 1619.4(3) pm, β = 96.52(2)°). In the dimeric unit [(TMTAT)₂Sm₂]^2? the Sm³⁺ ions are bonded to the four N atoms of the macrocyclic ligand and one C₆H₄ ring of the second ligand is attached η⁶ like to one metal ion. Additionally two [K(thf)₃]⁺ fragments are bonded to this central unit, and therefor coordination number seven results for the K⁺ ion. [TMTAA]^2? is not reduced by [Cp₂Co] in a similar reaction. The monomeric paramagnetic complex [(TMTAA)Co] (μ_eff = 2,76 μ_B) is formed instead. The structure reveils a square planar coordination of the Co atom by the four N atoms of the TMTAA ligand (spacegroup C2/c (No. 15), z = 4, a = 1945.1(4) pm, b = 1165.6(2) pm, c = 1144.7(2) pm, β = 116.38(1)°).     

Structural-dynamic approach and path analysis of the intramolecular electron transfer in the bridged complexes [(NH3)5Ru-py-(C2H2) n -py-Ru(NH3)5]5+ withn = 0,1,2,3

The electron interaction transfer paths in the mixed-valence complexes[(NH₃)₅Ru-py-(C₂H₂)_n-py-Ru(NH₃)₅]⁵⁺ are analyzed in the framework of perturbation theory. A structural-dynamic approach to treatment of the intramolecular electron transfer is proposed. This approach is based on the solution of the nonstationary Schrödinger equation in a basis of many-electron functions describing separate structural sites of the electron-transport chain Ry^II→pyridyl→ C₂H₂)_n→pyridyl→Ru^III.     

Synthese,Kristallstruktur und Magnetismus von [(CH3)2NH2][PrCl4(H2O)2]

Preparation, Crystal Structure, and Magnetism of [(CH₃)₂NH₂][PrCl₄(H₂O)₂] The complex water containing chloride [(CH₃)₂NH₂][PrCl₄(H₂O)₂] has been prepared for the first time and the crystal structure has been determined from single crystal X‐ray diffraction data. The compound crystallizes orthorhombically in the space group Cmca (Z = 8) with a = 1796.6(2) pm, b = 940.7(1) pm, and c = 1238.4(2) pm. The anionic part of the structure is built up by chains of edge‐connected trigondodecahedra [PrCl₆(H₂O)₂]^3– according to [PrCl_4/2Cl₂(H₂O)₂]^–, which are held together by dimethylammonium cations ([(CH₃)₂NH₂]⁺). In order to study the interactions between the praseodymium cation (Pr³⁺) and the ligands magnetic measurements were carried out. The magnetic data were interpreted by ligand field calculations applying the angular overlap model.     

Crystal Structure,Thermal and Electric Behaviour of [(CH3)2NH2]3[As2Cl9] and [(CH3)2NH2][AsOCl2]

Single crystals of the organic‐inorganic arsenate(III): [(CH₃)₂NH₂]₃[As₂Cl₉] and [(CH₃)₂NH₂][AsOCl₂] have been grown from aqueous hydrochloric acid solution. The crystals [(CH₃)₂NH₂]₃[As₂Cl₉] have been investigated by X‐ray diffraction (at 253 K), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dilatometric and dielectric methods. They undergo two structural phase transitions of first order at 228/235 and 298/307 K (on cooling/heating), respectively, which are classified as an "order‐disorder" type. The trigonal [(CH₃)₂NH₂]₃[As₂Cl₉] structure (at 253 K, intermediate phase (II)) refined in the space group R3c, consists of isolated [As₂Cl₉]^3‐ bioctahedral units and dimethylammonium cations hydrogen bonded to the bridging Cl atoms of the anions. The crystals of [(CH₃)₂NH₂][AsOCl₂] at 100 K are orthorhombic, space group Cmca. The structure contains one‐dimensional chains formed by strong distorted [AsO₂Cl₄] octahedra. The dimethylammonium cations reveal distinct disorder.     

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.     

Double complexes [Co(NH3)5(H2O)]2[Zr3F18]·6H2O and [Co(NH3)6]2[Zr3F18]·6H2O

The structures of orthorhombic bis[pentaammineaquacobalt(III)] tetra‐μ₂‐fluorido‐tetradecafluoridotrizirconium(IV) hexahydrate (space group Ibam), [Co(NH₃)₅(H₂O)]₂[Zr₃F₁₈]·6H₂O, (I), and bis[hexaamminecobalt(III)] tetra‐μ₂‐fluorido‐tetradecafluoridotrizirconium(IV) hexahydrate (space group Pnna), [Co(NH₃)₆]₂[Zr₃F₁₈]·6H₂O, (II), consist of complex [Co(NH₃)_x(H₂O)_y]³⁺ cations with either m [in (I)] or and 2 [in (II)] symmetry, [Zr₃F₁₈]⁶⁻ anionic chains located on sites with 222 [in (I)] or 2 [in (II)] symmetry, and water molecules.     

Darstellung und schwingungsspektroskopische Untersuchung von [H3B?Se?Se?BH3]2− und [H3B-μ2-Se(B2H5)]− Kristallstruktur und theoretische Untersuchung der Molekülstruktur von [H3B-μ2-Se(B2H5)]−

Synthesis and Vibrational Spectroscopic Investigation of [H₃B? Se? Se? BH₃]^2? and [H₃B-μ₂-Se(B₂H₅)]^? Crystal Structure and Theoretical Investigation of the Molecular Structure of [H₃B-μ₂-Se(B₂H₅)]^? M₂[H₃B? Se? Se? BH₃] 1 is produced by the reaction between elemental selenium and MBH₄ (1 : 1) in triglyme (diglyme), under dehydrogenation. 1 reacts with an excess of B₂H₆ to give M[H₃B-μ₂-Se(B₂H₅)] 2 which is also formed in the reaction of THF · BH₃ with 1 . These reactions proceed under cleavage of the Se? Se bond and hydrogen evolution. [(C₆H₅)₄]Br reacts with Na · 2 to form [(C₆H₅)₄P] · 2 which crystallizes in the tetragonal space group I4 (Nr. 82). An X-ray structure determination failed because of disordering of the cation and anion. ¹¹B, ⁷⁷Se NMR shifts and ¹J(¹¹B¹H) coupling constants as well as IR- and Raman spectroscopic investigations convey further structural information. Structural data of 2 have been calculated by SCF methods. The anion of 2 may be viewed either as an adduct of Se with B₃H₈^?, or as a bridge substituted selena derivative of B₂H₆.     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. 52. Darstellung,Charakterisierung und Reaktionen von (C5H5)3Ce · THF und Na[Ce(C5H5)4] · THF

Contributions to the Chemistry of Organo Transition Metal Compounds. 52. Preparation, Characterization, and Reactions of (C₅H₅)₃Ce · THF and Na[Ce(C₅H₅)₄] · THF (C₅H₅)₃ · THF ( I ) was synthesized in a simple manner by reaction of (NH₄)₂[Ce(NO₃)₆] with C₅H₅Na. With excess C₅H₅Na the complex Na[Ce(C₅H₅)₄] · THF ( II ) could be obtained. In addition of cyclovoltammetric and polarographic measurements it was tried without success to transfer I and II into organocerium( IV ) compounds by means of different oxidizing agents. II reacts with I₂ and (C₆H₅)₃CCl forming Na[(C₅H₅)₃CeI] · THF or Na[(C₅H₅)₂CeI₂] · 4 THF and I besides of (C₆H₅)₃CCl respectively. At interaction of I with Co(acac)₃ the cobalticinium salt [(C₅H₅)₂Co][C₅H₅Ce(acac)₃] is formed. The compounds obtained were characterized by elementary analysis, hydrolysis products, magnetic moments, i.r., ¹H-n.m.r. und u.v.-vis spectra, and measurements of electric conductivity.