Crystal structure of trans-pyH[MoBr4py2] and reactivity of Trans-pyH[MBr4py2] (M = Mo,W; py = pyridine) towards nitrogen ligands and bromine Oxidation

The crystal structure of trans-pyH[MoBr₄py₂] has been determined: orthorhombic, Pnma (No. 62), a = 16.197(3), b = 13.995(3), c = 8.615(1) Å, Z = 4, D_c = 2.23, D_o = 2.20(3) g/cm³, V = 1 953(1) ų. R₁, R_w = 0.057 and 0.053. Trans-[MoBr₄py₂]^? anions with staggered conformation of pyridine rings are located on the mirror planes. Mo? Br, Mo? N(pyridine) distances are 2.593(1), 2.573(1), 2.227(8) and 2.213(7) Å. Cations are located on the symmetry centers. The cation in trans-pyH[MBr₄py₂] can be replaced. Trans-NH₄[MBr₄py₂] · H₂O, Cs[MBr₄py₂], LH[MBr₄py₂] (M = Mo, W; L = 4-methylpyridine, 4-pic; 2,2′-bipyridyl, bipy) were prepared. The compounds of molybdenum and tungsten with the same chemical composition are isostructural. All compounds react with pyridine and 4-methylpyridine. The products are trans-MBr₃L₃, and in the case of molybdenum, also trans-MoBr₃py₂(4-pic). Bromine oxidizes trans-M^I[MBr₄py₂] to trans-MBr₄py₂.     

Synthesis of cis-Tetrabromobispyridinemolybdates(III) and the crystal structure of cis-(NH4)[MoBr4py2] · ⅓3 H2O (py = pyridine)

The reaction between (NH₄)[MoBr₅ · H₂O] and pyridine in acetonitrile (CH₃CN) at room temperature results in the mixture of cis- and trans-(pyH)[MoBr₄py₂] which can be separated on the basis of solubility. cis-M[MoBr₄py₂] · ? H₂O (M = NH₄⁺, Rb⁺, Cs⁺), cis-(bipyH)[MoBr₄py₂] (bipy = 2,2′-bipyridil) and cis-(PPh₄)[MoBr₄py₂], were prepared from cis-(pyH)[MoBr₄py₂]. At the temperature of boiling acetonitrile irreversible cis to trans isomerisation takes place. Bromine oxydizes cis isomers at room temperature to trans-MoBr₄py₂. The compounds were characterised by chemical analysis, infrared, UV-VIS spectroscopy, conductivity measurements and powder diffraction. The crystal structure of cis-(NH₄)[MoBr₄py₂] · ? H₂O has been determined: rhombohedral, R3c, (No. 161), a = 15.809(3) Å, β = 112.79(2)°, Z = 6, D_C = 2.29, D_O = 2.27(3) g/cm³, V = 2 601(1) ų, R₁ = 0.046, R_w = 0.068. Average Mo? Br and Mo? N(pyridine) distances within the anion are 2.58(2) and 2.20(2) Å. cis-Rb[MoBr₄py₂] · ? H₂O and cis-Cs[MoBr₄py₂] · ? H₂O are isostructural with cis-(NH₄)[MoBr₄py₂] · ? H₂O.     

Darstellung,Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalysen von trans-(PNP)[TcCl4(Py)2] und trans-(PNP)[TcBr4(Py)2]

Preparation, Crystal Structures, Vibrational Spectra, and Normal Coordinate Analysis of trans-(PNP)[TcCl₄(Py)₂] and trans-(PNP)[TcBr₄(Py)₂] By reaction of (PNP)₂[TcX₆] with pyridine in the presence of [BH₄]^? (PNP)[TcX₄(Py)₂], X = Cl, Br, are formed. X-ray structure determinations on single crystals of these isotypic Tc^III complexes (monoclinic, space group P2₁/n, Z = 2, for X = Cl: a = 13.676(4), b = 9.102(3), c = 17.144(2) Å, β = 91.159(1)°; for X = Br: a = 13.972(2), b = 9.146(3), c = 17.285(4) Å, β = 90.789(2)°) result in the averaged bond distances Tc? Cl: 2.386, Tc? Br: 2.519, Tc? N: 2.132(3) (X = Cl) and 2.143(4) Å (X = Br). The two pyridine rings are coplanar and vertical to the X? Tc? X-axes, forming angles of 42.28° (X = Cl) and 43.11° (X = Br). Using the molecular parameters of the X-ray structure determination and assuming D_2h point symmetry, the IR and Raman spectra are assigned by normal coordinate analysis based on a modified valence force field. Good agreement between observed and calculated frequencies is obtained with the valence force constants f_d(TcCl) = 1.45, f_d(TcBr) = 1.035, f_d(TcN) = 1.37 (X = Cl) and 1.45 mdyn/ Å (X = Br), respectively.     

Darstellung der Halogeno-Pyridin-Rhenate(III), [ReX6−n (Py)n](3−n)− (X = Br,Cl; n = 1−3), sowie Kristallstrukturen von trans-[(C4H9)4N][ReBr4(Py)2], mer-[ReCl3(Py)3] und mer-[ReBr3(Py)3]

Preparation of Halogeno Pyridine Rhenates(III), [ReX_6?n(Py)_n]^(3?n)? (X = Br, Cl; n = 1?3) Crystal Structures of trans-[(C₄H₉)₄N][ReBr₄(Py)₂], mer-[ReCl₃(Py)₃], and mer- [ReBr₃(Py)₃] The mixed halogeno-pyridine-rhenates(III), [ReX_6?n(Py)_n]^(3?n)? (X = Br, Cl), n = 1?3, have been prepared for the first time by reaction of the tetrabutylammoniumsalts (TBA)₂[ReX₆] (X = Br, Cl) in pyridine with (TBA)BH₄ and separation by chromatography on Al₂O₃. Apart from the monopyridine complexes only the trans and mer isomers are formed from the bis-and tris-pyridine compounds. The X-ray structure determinations of the isotypic neutral complexes mer- [ReX₃(Py)₃] (monoclinic, space group P 2₁/n, Z = 4; for X = Cl: a = 9,1120(8), b = 12,5156(14), c = 15,6100(13) Å, β = 91,385(7)°; for X = Br: a = 9,152(5), b = 12,852(13), c = 15,669(2) Å, β = 90,43(2)°) reveal, due to the stronger trans influence of pyridine compared with Cl and Br, that the Re? X distances in asymmetric Py? Re? X3 axes with ReCl3 = 2,397 Å and ReBr3 = 2,534 Å are elongated by 1,3 and 1% in comparison with symmetric X1? Re? X2 axes with ReCl1 = ReCl2 = 2,367 Å and ReBr1 = 2,513 and ReBr2 = 2,506 Å, respectively. The Re? N bond lengths are roughly equal with 2,12 Å. Trans-(TBA)[ReBr₄(Py)₂] crystallizes triclinic, space group P1 , a = 9,2048(12), b = 12,0792(11), c = 15,525(2) Å, α = 95,239(10), β = 94,193(11), γ = 106,153(9)°, Z = 2. The unit cell contains two independent but very similar complex anions with approximate D_2h(mmm) point symmetry.     

Room Temperature Synthesis and Crystal Structure of mer‐[MoBr3Py3], the Vibrational Spectra of mer‐[MoBr3Py3], mer‐[MoI3Py3] and trans,trans‐[MoBr2Py4][MoBr4Py2]

The reaction of MoBr₃ and pyridine at room temperature provided single crystals of mer‐[MoX₃Py₃]. mer‐[MoBr₃Py₃] crystallizes in P2₁/n monoclinic space group with cell dimensions a = 9.2297(5) Å, b = 12.911(8) Å, c = 15.7022(9) Å and β = 90.479(3)°. There are four formula units in a unit cell. Mo–N distances are in the range 2.196(8)–2.214(8) Å and Mo–Br distances are 2.573(1) Å and 2.574(1) Å. Fundamental vibrational frequencies of pyridine molecules are strongly affected upon coordination in all three coordination compounds: mer‐[MoBr₃Py₃], mer‐[MoI₃Py₃] and trans,trans‐[MoBr₂Py₄][MoBr₄Py₂].     

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.     

Kristallstruktur von Dipyridiniomethan-Monohalogenohydro-closo-Decaboraten(2–), [(C5H5N)2CH2][2-XB10H9]; X  Cl,Br, I

Crystal Structures of Dipyridiniomethane Monohalogenohydro-closo-Decaborates(2–), [(C₅H₅N)₂CH₂][2-XB₁₀H₉]; X = Cl, Br, I [B₁₀H₁₀]^2? reacts with chlorine, bromine and iodine or with N-halogenosuccinimide, yielding the monohalogenodecaborates [2-XB₁₀H₉]^2? (X = Cl, Br, I), which are separated by ion exchange chromatography on diethylaminoethyl(DEAE) cellulose from the starting compound and higher halogenated products. The X-ray structure determinations of the isotypic chloro and bromo compounds [(C₅H₅N)₂CH₂][2-XB₁₀H₉] (monoclinic, space group C2/c, Z = 8; for X ? Cl: a = 33.174(5), b = 7.2809(4), c = 16.2232(7) Å, β = 113.307(7)°; for X = Br: a = 33.525(11), b = 7.281(2), c = 16.297(4) Å, β = 113.62(2)°) and of the iodo compound [(C₅H₅N)₂CH₂][2-IB₁₀H₉] (monoclinic, space group P2₁, Z = 2, a = 7.143(3), b = 13.568(4), c = 9.479(7) Å, β = 97.57(5)°) show columns of substituted boron clusters [2-XB₁₀H₉]^2?, X = Cl, Br, I and bent dications [(C₅H₅N)₂CH₂]²⁺ along the shortest axis wich are assembled to alternating layers in the crystal lattice.     

Darstellung und Kristallstrukturen von Dipyridiniomethan-Monohalogenohydro-closo-Dodecaboraten(2−), [(C5H5N)2CH2][B12H11X]; X = Cl,Br, I

Preparation and Crystal Structures of Dipyridiniomethane Monohalogenohydro-closo-Dodecaborates(2?), [(C₅H₅N)₂CH₂][B₁₂H₁₁X]; X = Cl, Br, I [B₁₂H₁₂]^2? reacts with dihalogenomethanes CH₂X₂ in presence of trifluoro acetic acid, yielding the monohalogenododecaborates [B₁₂H₁₁X]^2? (X = Cl, Br, I), which are separated by ion exchange chromatography on diethylaminoethyl(DEAE) cellulose from the starting compound and higher halogenated products. The X-ray structure determinations of [(C₅H₅N)₂CH₂][B₁₂H₁₁Cl] · 2(CH₃)₂SO (orthorhombic, space group Pnma, a = 17.351(6), b = 16.034(5), c = 9.659(2) Å, Z = 4) and of the isotypic bromo and iodo compounds [(C₅H₅N)₂CH₂][B₁₂H₁₁X] (monoclinic, space group P2₁/n, Z = 4; for X = Br: a = 7.339(2), b = 15.275(3), c = 16.761(4) Å, β = 96.80(2)°; for X = I: a = 7.4436(8), b = 15.3510(8), c = 16.9213(16) Å, ß = 97.326(7)°) exhibit crystal lattices build up by columns of substituted boron clusters and angular dications [(C₅H₅N)₂CH₂]²⁺ orientated along the shortest axis which are assembled to alternating layers.     

Darstellung und Charakterisierung von [Pt(mal)2]2− und von trans-[Pt(mal)2X2]2− (X = Cl,Br, I,SCN)

Preparation and Characterization of [Pt(mal)₂]^2? and trans-[Pt(mal)₂X₂]^2? (X = Cl, Br, I, SCN) By twofold treatment of K₂[PtCl₄] with potassium hydrogen malonate in a queous solution the yellow K₂[Pt(mal)₂] · H₂O is obtained. After extraction with tetrabutylammonium ions into dichloromethane by oxidative addition at ?90°C the Pt^IV complexes [Pt(mal)₂X₂]^2?, X = Cl, Br, I, SCN, are formed. The SCN ligands are coordinated to Pt via S. The IR and Raman spectra are discussed and assigned.     

Darstellung,Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalyse von [PtX2ox]2−, X = Cl,Br

Synthesis, Crystal Structure, Vibrational Spectra, and Normal Coordinate Analysis of [PtX₂ox]²⁻, X = Cl, Br By treatment of [PtX₄]^2— (X = Cl, Br) with C₂O₄^2— (ox^2—) in water [PtCl₂ox]^2— and [PtBr₂ox]^2— are formed which have been isolated by ion exchange chromatography on diethylaminoethyl cellulose. The crystal structures of [(C₅H₅N)₂CH₂][PtCl₂ox]·2H₂O ( 1 ) (orthorhombic, space group Pbca, a = 18.451(1), b = 18.256(1), c = 19.913(1)Å, Z = 16) and [(C₅H₅N)₂CH₂][PtBr₂ox] ( 2 ) (monoclinic, space group P2₁/c, a = 7.249(1), b = 10.180(1), c = 21.376(1)Å, β = 93.415(9)°, Z = 4) reveal nearly planar complex anions with C_2v point symmetry. The bond lengths are Pt‐Cl = 2.286, Pt‐Br = 2.405 und Pt‐O = 2.016 ( 1 ) und 2.030Å ( 2 ). In the vibrational spectra the PtX stretching vibrations are observed at 335 and 336 ( 1 ) and 219 and 231 cm^—1 ( 2 ). The PtO stretching vibrations are coupled with internal modes of the oxalato ligands and appear in the range of 350 — 800 cm^—1. Using the molecular parameters of the X‐Ray determinations the IR and Raman spectra of the (n‐Bu₄N) salts are assigned by normal coordinate analysis. The valence force constants are f_d(PtCl) = 1.97, f_d(PtBr) = 1.78 and f_d(PtO) = 2.48 ( 1 ) and 2.38 mdyn/Å ( 2 ). Taking into account increments of the trans influence a good agreement between observed and calculated frequencies is achieved. The NMR shifts are δ(¹⁹⁵Pt) = 3603.9 ( 1 ) and 3318.1 ppm ( 2 ).     

Reactions of Hexanuclear Niobium and Tantalum Halide Clusters with Mercury(II) Halides. I. Synthesis and structures of the semiconducting compounds [M6Br12(H2O)6][HgBr4] · 12H2O,MNb,Ta

A method for the preparation of new solvated clusters of the composition [M₆Br₁₂(H₂O)₆][HgBr₂X₂] · 12H₂O (M?Nb, Ta; X?Cl, Br, I) is given. The cubic crystals of [Nb₆Br₁₂(H₂O)₆][HgBr₄] · 12H₂O 1 and [Ta₆Br₁₂(H₂O)₆][HgBr₄] · 12H₂O 2 were characterized by the X-ray structure analysis: 1 : cubic, space group Fd3 m, a = 21.0072(6) Å, Z = 8, R = 0.051 (R_w = 0.066); 2 : cubic, space group Fd3 m, a = 20.9698(1) Å, Z = 8, R = 0.038 (R_w = 0.050). 1 and 2 contain octahedral cluster cation [M₆Br₁₂(H₂O)₆]²⁺ and tetrahedrally arranged [HgBr₄]^2? anion. The M? M bond distances are 2.949(1) Å for 1 and 2.9000(8) Å for 2 . The Hg? Br bond distances in [HgBr₄]^2? anion are 2.614(2) Å in 1 and 2.622(2) Å in 2 . The crystal packing patterns of the isostructural clusters 1 and 2 involve the three-dimensional hydrogen bond network; the crystalline water molecules act as donors of hydrogen to the bromine atoms of the cluster and [HgBr₄]^2? units, whereas the coordinated water molecules form hydrogen bonds to the crystalline water molecules. [Nb₆Br₁₂(H₂O)₆][HgBr₄] · 12H₂O is diamagnetic and semiconducting with the activation energy, E_a = 0.20 eV.     

Halogenomercurate: Darstellung und Strukturen von [Cu(en)2][Hg2Cl6], [Cu(en)2][Hg2Br6] und [Cu(en)2][HgBr4]

Halomercurates: Syntheses and Crystal Structures of [Cu(en)₂][Hg₂Cl₆], [Cu(en)₂][Hg₂Br₆], and [Cu(en)₂][HgBr₄] Crystals of [Cu(en)₂][Hg₂Cl₆] ( 1 ) have been obtained by layering a solution of Hg(NO₃)₂ and NaCl with a solution of [Cu(en)₂]SO₄. An analogous procedure, using NaBr instead of NaCl, gave crystals of [Cu(en)₂][HgBr₄] ( 3 ). Crystals of [Cu(en)₂][Hg₂Br₆] ( 2 ) were obtained by gel crystallization using the same starting materials as for 3 . The complexes show very low solubility. The dinuclear anions of 1 consist of two nearly planar HgCl₃ units related by a center of symmetry. In 2 infinite anionic chains are present, made up of parallel HgBr₃ units. These units are packed in such a way as to produce a trigonal bipyramidal configuration around the Hg atoms. 3 contains mononuclear deformed tetrahedral [HgBr₄]^2– anions. In all three complexes the packing of the ions is such that halogen atoms of halomercurate anions complete a tetragonal bipyramidal coordination at Cu. The resulting Cu–Halogen distances are 2.924 Å for 1 , 3.036 Å for 2 and 3.085 and 3.119 Å for 3 . 1 : Space group P 1, Z = 1, lattice constants at 20 °C: a = 7.000(2), b = 7.526(2), c = 8.239(2) Å; α = 88.39(2), β = 86.06(2), γ = 86.10(3)°; R₁ = 0.040. 2 : Space group P2₁/c, Z = 2, lattice constants at –50 °C: a = 7.185(1), b = 16.338(2), c = 7.814(1) Å; β = 94.88(2)°; R₁ = 0.033. 3 : Space group P2₁/n, Z = 4, lattice constants at 20 °C: a = 8.055(3), b = 13.101(3), c = 13.814(3) Å; β = 91.24(3)°; R₁ = 0.092.     

Pb2PdX6 (X = Cl,Br) – Verbindungen mit gestreckten [PdX6]-Oktaedern

Pb₂PdX₆ (X = Cl, Br) – Compounds with Elongated [PdX₆] Octahedra In contradiction to published data new compounds in the systems PbX₂—PdX₂ (X = Cl, Br) with the formula Pb₂PdCl₆ (I) and Pb₂PdBr₆ (II) were found. These were synthesized by thermal treatment of the corresponding mixtures of PbX₂ and PdX₂ (X = Cl, Br). X-ray single crystal structure analysis shows isotypism of I and II, monoclinic, P2₁/c (No. 14), Z = 2, I: a = 9.037(2) Å, b = 6.224(1) Å, c = 8.162(1) Å, β = 90.31(7)β, II: a = 9.512(7) Å, b = 6.584(8) Å, c = 8.383(3) Å, β = 90.07(5)º. Strongly elongated PdX₆ octahedra are found in the crystal structure. Additional characterisation of the compounds was done by DTA, IR/RAMAN spectra and ²⁰⁷Pb MAS NMR investigations. Remarcable low field shifts were found for ²⁰⁷Pb.     

Reactions of halogens with platinum(IV) triamine complexes [PtEnPyX3]X (X = Cl, Br)

Platinum(IV) complexes of the tetramine type [PtEnPy₂X₂]X₂ · H₂O (X = Cl, Br) have been found to lose a coordinated pyridine molecule at 125–135°C, thereby transforming into triamines [PtEnPyX₃]X. The complex [PtEnPyCl₃]NO₃ has been isolated. Dissolution of the product of [PtEnPy₂Cl₂]Cl₂ chlorination in HCl results in complete destruction of the five-membered chelate ring. The complex [Pt(NH₃)₂Py₂Cl₂](NO₃)₂ has been isolated. A number of compounds have been studied by X-ray diffraction: [PtEnPy₂Cl₂]Cl₂ · 2H₂O (I) (monoclinic, space group P2₁/c, a = 15.418(2) Å, b = 9.203(1) Å, c = 13.762(3) Å, β = 104.18(2)°, Z = 4, R _hkl = 0.25), [PtEnPyCl₃]NO₃ (II) (monoclinic, space group P2₁/c, a = 8.194(1) Å, b = 8.846(1) Å, c = 19.855(2) Å, β = 97.10(1)°, Z = 4, R _hkl = 0.048), and [Pt(NH₃)₂Py₂Cl₂](NO₃)₂ (III) (orthorhombic, space group Pbca, a = 12.316(2) Å, b = 13.250(3) Å, c = 21.868(4) Å, Z = 8, R _hkl = 0.027). The reaction of [PtEnPyBr₃]Br with bromine gives the polybromide [PtEnPyBr₃]Br · Br₂ · 0.5 H₂O. The chlorination of [PtEnPyCl₃]Cl gives the chloramine complex [Pt(NH₂-CH₂-NH(Cl)PyCl₃]Cl · H₂O.     

Magnesiumphthalocyanine: Darstellung und Eigenschaften von Halogenophthalocyaninatomagnesat, [Mg(X)Pc2−]− (X = F,Cl, Br); Kristallstruktur von Bis(triphenylphosphin)iminiumchloro(phthalocyaninato)magnesat-Aceton-Solvat

Magnesium Phthalocyanines: Synthesis and Properties of Halophthalocyaninatomagnesate, [Mg(X)Pc^2?]^? (X = F, Cl, Br); Crystal Structure of Bis(triphenylphosphine)iminiumchloro-(phthalocyaninato)magnesate Acetone Solvate Magnesium phthalocyanine reacts with excess tetra(n-butyl)ammonium- or bis(triphenylphosphine)iminiumhalide ((ⁿBu₄N)X or (PNP)X; X = F, Cl, Br) yielding halophthalocyaninatomagnesate ([Mg(X)Pc^2?]^?; X = F, Cl, Br), which crystallizes in part as a scarcely soluble (ⁿBu₄N) or (PNP) complex-salt. Single-crystal X-ray diffraction analysis of ^b(PNP)[Mg(Cl)Pc^2?] · CH₃COCH₃ reveals that the Mg atom has a tetragonal pyramidal coordination geometry with the Mg atom displaced out of the center (Ct) of the inner nitrogen atoms (N_iso) of the nonplanar Pc ligand toward the Cl atom (d(Mg? Ct) = 0.572(3) Å; d(Mg? Cl) = 2.367(2) Å). The average Mg? N_iso distance is 2.058 Å. Pairs of partially overlapping anions are present. The cation adopts a bent conformation (^b(PNP)⁺: d(P1? N(K)) = 1.568(3) Å; d(P2? N(K)) = 1.587(3) Å; ?(P1? N(K)? P2) = 141.3(2)°). Electrochemical and spectroscopic properties are discussed.     

Darstellung und Schwingungsspektren von trans-[Pt(acac)2X2] (X  Cl,Br, I,SCN, SeCN,N3)

Preparation and Vibrational Spectra of trans-[Pt(acac)₂X₂] (X ? Cl, Br, I, SCN, SeCN, N₃) By electrolytical oxidation of [Pt(acac)₂] in presence of chloride or bromide, dissolved in dichlormethane, trans-[Pt(acac)₂X₂], X ? Cl, Br, are formed. On treatment of trans-[Pt(acac)₂I₂] with silver pseudohalides trans-[Pt(acac)₂X₂], X ? SCN, SeCN, N₃, are obtained. Beside the nearly persistent bands of coordinated acetylacetonate in the Raman spectra the intensive and sharp symmetric, in the IR spectra the corresponding antisymmetric stretching vibration of the X? Pt? X axis is observed. The observance of the rule of mutual exclusion proves the complexes to belong to point group D_2h. From the resonance Raman spectrum of trans-[Pt(acac)₂I₂] for v_s (Pt? I), A_g, the harmonic frequency ω₁ = 142.45 cm^?1 and the inharmonicity constant x₁₁ = 0.48 cm^?1 is calculated. In the Raman spectrum of trans-[Pt(acac)₂Cl₂] v_s (Pt? Cl) is splitted by the isotops ³⁵Cl/³⁷Cl into the triplet 340, 335, 330 cm^?1 giving the force constant f_PtCl = 2.01 N/cm.     

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.     

Magnetic and spectroscopic properties of [Co(AGlH)2py2][Cr(NH3)2NCS)4] and [Co(AGlH)2py2][Co(NH3)2(NO2)4] complexes

The magnetic and spectroscopic (UV, visible-IR and electron paramagnetic resonance spectra) properties of the molecular complexes [Co(AGlH)₂py₂][Cr(NH₃)₂(NCS)₄] and [Co(AGlH)₂py₂][Co(NH₃)₂(NO₂)₄] (where AGlH₂ is diaminoglyoxime) have been examined in solid state. The molecular structure of the complexes and the nature of the interaction in the crystals has been considered.     

Direct Syntheses of Bis(tetraphenylphosphonium) and Bis(ethyltriphenylphosphonium) Hexabromo‐diselenates(II), [PPh4]2[Se2Br6] and [PEtPh3]2[Se2Br6]. The Crystal Structure of [PEtPh3]2[Se2Br6]

Brown crystals of [PPh₄]₂[Se₂Br₆] ( 1 ) and [PEtPh₃]₂[Se₂Br₆] ( 2 ) were obtained when selenium and bromine reacted in acetonitrile solution in the presence of tetraphenylphosphonium bromide and ethyltriphenylphosphonium bromide, respectively. The crystal structure of 2 has been determined by X‐ray methods and refined to R = 0.0420 for 4161 reflections. The crystals are monoclinic, space group P2₁/n with Z = 2 and a = 13.055(3) Å, b = 12.628(3) Å, c = 13.530(3) Å, β = 92.40(3)° (293(2) K). In the solid state structure of 2 the dinuclear hexabromo‐diselenate(II) anion is centrosymmetric and consists of two distorted almost square‐planar SeBr₄ units sharing a common edge through two bridging Br atoms. The terminal Se^II–Br bond distances are found to be 2.419(1) and 2.445(1) Å, the bridging μBr–Se^II bond distances 2.901(1) and 2.802(1) Å.     

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.