bluuebunny/crossref_metadata_2025 huggingface dataset:
Zur Stereochemie von Iodoarsenaten(III). Darstellung und Kristallstrukturen von [nBU4N]2[AS2I8], [pyH][AsI4] und [Et3NH]4[As8I28] / Concerning the Stereochemistry of Iodoarsenates(III). Preparation and Crystal Structures of [nBu4N]2[As2I8], [pyH][AsI4] and [Et3NH]4[As8I28]
Authors: Sheldrick W. S. , Häusler H.-J. , Kaub J.
Published: March 2015

[nBU4N]2[AS2I8] (1), [pyH][AsI4] (2) and [Et3NH]4[As8I28] (3) have been prepared hy reaction of Asl3 with the iodide of the respective nitrogen base (present in a 1:1 molecular ratio) in acetonitrile and their structures determined by X-ray structural analysis. 1 contains discrete [As2I8]2- anions with Q symmetry; the As atoms display a pseudo-octahedral AX4Y'E geometry with bridging A s - I distances of 2.931(1) and 3.289(1) Å. The iodoarsenate(III) anions in 2 form infinite [Asl4
-]∞ chains, in which the individual units are edge-bridged distorted AsI6-octahedra with AX4Y'2E geometry. In contrast, 3 contains discrete centrosymmetric anions [As8I28]4-. in which the individual As atoms all display a distorted octahedral AX,Y,E geometry. The lone pairs are stereochemically inert in 2 and 3. The structures of 1-3 are compared with those of analogous chloro- and bromoarsenate(III) anions.
Reaktionen von Zintl-Phasen mit Trimethylphosphinkomplexen Strukturen mit ebenem Vierring Co2X2 (X = S, Se, Te) / Reactions of Zintl-Phases with Trimethylphosphine Complexes Structures Containing Planar Metallocycles Co2X2 (X = S. Se. Te)
Authors: Klein Hans-Friedrich , Gaß Michael , Koch Udo , Eisenmann Brigitte , Schäfer Herbert
Published: March 2015

Low-valent trimethylphosphine cobalt compounds are oxidized by tellurium, selenium, or sulfur to give the title compounds. Several high-yield syntheses are described. The crystal and molecular structures of (Me3P)3CoX3Co(PMe3)3 (1: X = Te. 2: X = Se. 3: X = S) have been determined by single crystal X-ray diffraction. Complex 1 crystallizes in the monoclinic space group P21/n; a = 933.8(6) pm. b = 1488.3(6) pm. c = 1257.9(6) pm. β = 92.82(6)°. Z = 2.

Complex 2 crystallizes in the triclinic space group P1, a = 1785.6(7) pm. b = 1599.7(7) pm. c = 928.9(5) pm. α = 87.8(1)°. β = 85.2(1)°. γ = 73.3(1)°. Z = 3.

Complex 3 crystallizes in the monoclinic space group P21/c; a = 952.6(5) pm. b = 1868.7(8) pm. c - 1893.1(8) pm. β = 90.19(6)°. Z = 4.

All three structures contain centrosymmetric molecules with planar Co2X2 rings. In solution dissociation of phosphine ligands occurs followed by slow decomposition to produce [(Me3P)2Co(PMe2)]2 among other products. 1 reacts with carbon monoxide to afford a ditelluride [(Me3P)2(CO)2Co]2Te2. but no corresponding derivatives of 2 or 3 were obtained.
Cyclobutadien-homologe Diazadiboretidine als Liganden von Übergangsmetallen / Cyclobutadiene-Homologous Diazadiboretidines as Ligands to Transition Metals
Authors: Paetzold Peter , Delpy Klaus , Boese Roland
Published: March 2015

The sandwich type product CpCoL (1c) and the carbonyl species (OC)3FeL (2c), (OC)4CrL (3e), (OC)4MOL (4b), and (OC)4WL (5b) were prepared with diazadiboretidines (RBNR′) : (L) as tetra-hapto ligands (a-d: R = Me, Et, Pr. Bu; R′ = tBu; e: R = R′ = iPr). The ligand (iPrBNiPr)2 , prepared by a novel catalytic cyclodimerisation of iPrB≡NiPr, undergoes subsequent cyclodimerisation to the eight-membered ring (iPrBNiPr)4 at ambient temperature, where-as the corresponding cycloreversion occurs at 100 °C. The structure of the complexes (OC)xML is discussed by means of IR and NMR data and the structures of crystalline 2c and 5d were determined by X-ray crystallography.
Structure of a New Eudesmane Sesquiterpene Argutinin from Pluchea arguta Boiss
Authors: Ahmad Viqar Uddin , Fizza Kaniz
Published: March 2015

A new eudesmane sesquiterpene, argutinin (1) has been isolated from Pluchea arguta Boiss. Its structure has been elucidated by spectroscopic methods.
Molekülstruktur von (o-Trimethylsilylbenzyl) diphenylphosphan / Molecular Structure of (o-Trimethylsilylbenzyl) diphenylphosphine
Authors: Reber Gabi , Riede Jürgen , Müller Gerhard
Published: March 2015

(o-Trimethylsilylbenzyl)diphenylphosphine (1) crystallizes in the monoclinic space group P21/n with a = 14.088(2), b = 8.712(1), c = 16.481(2)Å, β = 101.63(1)°, V -1981.3 Å3 Z = 4. There is no P-Si interaction in the solid state which is also found for the solution (31P NMR, 13C NMR).
Polymorphie von Tellur(IV)-iodid/ Polymorphism of Tellurium(IV) Iodide
Authors: Kniep Rüdiger , Beister Heinz Jürgen , Wald Dieter
Published: March 2015

Idiomorphous crystals of five different polymorphic modifications (α-ε) of TeI4 are simultaneously grown from solutions of TeI4 and concentrated HI in methanol by evaporating the solvent at room temperature. δ-TeI4 is the only stable phase at normal conditions. Phase transformations of α-, β-, γ-and ε-TeI4 to the final stage δ-TeI4 take place by heating and run through discrete intermediates. The observed graduations lead to a sequence γ-, β-, α-,ε-TeI4 which indicates “increasing metastability”. The crystal structures of α-TeI4 (trigonal; P3̄ml; a = 4.228(2), c - 6.684(6)Å, Z = 0.5; Dx = 5.10 g/cm 3), β-TeI4 (orthorhombic; Pn21m; a = 6.888(2), b = 14.539(3), c = 16.753(4) Å, Z = 8; Dx = 5.03 g/cm3) and γ-TeI4 (monoclinic; P21/c; a = 11.199(4), b = 13.599(4), c = 22.158(6) Å,β = 98.10(3)°, Z = 16; D, = 5.05 g/cm3) are related to the known crystal structure of δ-TeI4. α-TeI4 (“Te0.5I2”) is an isotype of the 2H-CdI : structure with random distribution of Te over the Cd-positions. The crystal structures of β-, γ-and δ-TeI 4 contain discrete tetrameric molecules “(TeI4)2 (TeI3
+I-)2” which are generated by ordered distributions of Te over 1/4 of the octahedral holes of a 2H-(β) and a 4H-sequence (y,δ ) of the nearly close packed iodine layers. A nearly cubic close packing of Iodine atoms is observed in the crystal structure of ε-TeI4 (tetragonal; I41/amd; a = 16.875(6), c -11.829(5) Å, Z = 16; Dx = 5.01 g/cm 3). The ordered distribution of Te in 1/4 of the octahedral holes leads to tetrameric molecules “(TeI3
+I-)4” in a cubanelike arrangement which, thus far, has been observed only in the crystal structures of TeCl4 and TeBr4 . The Madelung Parts of Lattice Energies, MAPLE, of β-, γ-, δ-and ε-TeI4 are calculated.
Synthese, Eigenschaften und Kristallstruktur von (NH4)NbOBr4/ Synthesis, Properties and Crystal Structure of (NH4)NbOBr4
Authors: Hörner Manfredo , Hiller Wolfgang , Strähle Joachim , Sheldrick George M.
Published: March 2015

(NH4)NbOBr4 is obtained as air sensitive, light red crystals from NH4Br and NbBr 5 in a sealed glass ampoule at 420 °C, whereby the oxygen presumably originates from the glass surface. The compound crystallizes in the monoclinic space group C2/m with a = 1269.9(1), b = 1384.7(2). c = 773.0(2) pm, β = 114.44(2)° and Z = 6.

The structure is built up by NH4+ cations and polymeric NbOBr4 anions. Symmetrical linear oxo bridges with Nb-O = 199 pm connect square planar NbBr4 units to form endless chains arranged in planes parallel (010). Neighbouring NbBr4 units are in eclipsed as well as staggered orientations. The NH4
+ cations are located between the planes of parallel NbOBr4
- chains. The vibrational frequencies of the IR and Raman spectrum are assigned.
Zur Stereochemie des freien Elektronenpaares in AX6E-Systemen, VIII. Statisch verzerrte Anionen in [H3N(CH2)3NH3]3(BiX6)2(H2O)2 mit X = Cl, Br/ On the Stereochemistry of the Lone-Pair Electrons in AX6E-Systems, VIII Statically Distorted Anion in [H3N(CH2)3NH3]3(BiX6)2(H2O)2 with X = Cl, Br
Authors: Bois André du , Abriel Walter
Published: March 2015

Using 293 K diffractometer intensity data, the crystal structures of [H3N(CH2)3NH3]3(BiX6)2(H2O)2 with X - Cl, Br have been determined by single crystal X-ray technique and refined to a final Rw of 0.027 and 0.043, respectively. The structures are isotypic, space group P21/c, Z = 2 with a = 14.415(1). b = 9.7401(7), c = 12.4609(9)Å, β = 105.997(8)°for X - Cl and a = 14.794(2), b = 10.127(2), c = 12.853(2)Å, β = 105.68(2)° for X - Br. Statically distorted BiX6
3- octahedra confirm the symmetry rules for the stereochemistry of the lone pair electrons in AX6E-systems. Basic structural data for all compounds containing BiX6
3- and SbXh3 ions (X = Cl, Br, I) known to date are given including the ⊿-values as a measure for the distortion of the octahedral coordination polyhedron.
[Fe(phen)3]2Sb6l22·2CH3CN: Ein Iodoantimonat mit zentralem [Sb6I6]-Doppelwürfel (phen = 1,10-Phenanthrolin)/ [Fe(phen)3]2Sb6I22 · 2 CH3CN: An Iodoantimonate with Central [Sb6I6]-Double Cube (phen = 1,10-Phenanthrolin)
Authors: Pohl Siegfried , Haase Detlev , Lötz Rainer , Saak Wolfgang
Published: March 2015

Reaction of [Fe(phen)3]I2 (phen = 1.10-Phenanthrolin) with Sbl3 in acetonitrile leads to [Fe(phen)3]2Sb6I22·2CH3CN (1). The structure of 1 was determined from single crystal X-ray diffraction data.

1 crystallizes in the triclinic space group P1̄ with a = 1352.4(1). b - 1376.8(1), c - 1597.7(1) pm, α = 105.85(1). β = 92.09(1). γ = 97.94(1)°. Z = 1. The structure of 1 consists of isolated anions and cations.

The centrosymmetric Sb6I22
4- ion exhibits a double cube-like structure with Sb and I occupying alternating corners of the skeleton.
Nicotinamide Nucleotides in Different Types of Human Cataractous Lenses
Authors: Sarwat Tanweer , Rahman M. Ataur , Kirmani T. H.
Published: March 2015

The ratios of reduced and oxidized nicotinamide nucleotides (NADH/NAD+ and NADPH/ NADP+) were indirectly determined at various stages of cataractogenesis by estimating the concentrations of metabolites (lactate, pyruvate and malate) of the lens. The ratios of NADH/NAD+ and NADPH/NADP+ decreased significantly from immature to mature (P<.001, P<.05). to hypermature (P<.001, P<.05), to Morgagnian (Pc.001. Pc.001) and diabetic types (Pc.001, P < .001) of cataractous lenses respectively. Ratios of nicotinamide nucleotides in diabetic lenses were lower in comparison to those of other types studied. As the opacity progressed, the ratios decreased with increase in blood glucose levels.
Notizen: Synthese und Kristallstruktur von PPh3Me[HSO4]/ Synthesis and Crystal Structure of PPh3Me[HSO4]
Authors: Schmock Fritjof , Müller Aida , Müller Ulrich , Dehnicke Kurt
Published: March 2015

PPh3Me[HSO4] was prepared by the reaction of (PPh3Me)I with silver sulfate in aqueous solution. OPPh2Me and benzene being the by-products. The title compound was characterized by its IR spectrum as well as by an X-ray structure determination (1730 observed independent reflexions, R = 0.043). Crystal data: a = 910.4(3). b = 1587.8(4), c = 1294.2(6) pm, β = 105.52(3)°. space group P21/c, Z = 4. The structure consists of PPh3Me⊕ cations and of HOSO3
⊖ ions that are associated via strong hydrogen bonds to dimeric centrosymmetric units.
Synthesen und Strukturen der sterisch überladenen Disiloxane und Disilazane (tBu3 Si)2O, (tBu3Si)2NH, (tBu3SiNHSitBu2)2O [1]
Authors: Wiberg Nils , Kühnel Edwin , Schurz Klaus , Borrmann Horst , Simon Arndt
Published: March 2015

Hexa-terf-butyldisiloxane (tBu3Si)2O (2), hexa-rerr-butyldisilazane (tBu3Si)2NH (3), and the disiloxane (tBu3SiNHSuBu2)2O (4) are prepared from bis(silyl)triazene tBu3SiN=N-NHSirBu3 by reaction with water (2) and by thermolysis (3), or from silanimine tBu2Si=NSirBu3 by reaction with water (4). Structures of 2-4 have been determined by X-ray crystallography (for data cf. Tables II). As a consequence of the bulkiness of the silyl groups, the heavy atom frameworks SiOSi in 2 and 4 are linear, and the SiNSi angles in 3 (167 ± 2°) and 4 (157.1°) are comparatively large.
Synthese und Kristallstrukturen der spirocyclischen Polyselenido-Komplexe [Na-15-Krone-5]2[M(Se 4)2] mit M = Zink, Cadmium und Quecksilber
Authors: Adel Jörg , Weller Frank , Dehnicke Kurt
Published: March 2015

The title compounds have been prepared by reactions of the metal acetates of zink, cadmium, and mercury with ethanolic solutions of sodium polyselenides in the presence of 15-crown-5. They form dark red crystals, which were characterized by their IR specta as well as by X-ray crystal structure determinations. All complexes [Na-15-crown-5]2[M(Se 4)2] with M = Zn (1), Cd (2), Hg (3) crystallize isotypically in the space group C2/c with 4 formula units per unit cell. In the anions [M(Se4)2]2- the metal atoms are coordinated tetrahedrally by four selenium atoms of two Se4
2- units, thus forming a spiro-bicyclus. The complex cations [Na-15-crown-5]+ have a Na---Se contact of approximately 299 pm with two selenium atoms of a MSe4 group, allowing formulation of triple ion species.
Iodoantimonate der Zusammensetzung A+Sb2I7
- : Diskrete Anionen in (Me4N)4Sb8I28 und (Me3S)4Sb8I28 , polymere Ketten in (Me3NCH2Ph)Sb2I7 (Me = CH3 , Ph = C6H5 )
Authors: Pohl Siegfried , Lötz Rainer , Haase Detlev , Saak Wolfgang
Published: March 2015

The reaction of SbI3 with Me4NI, Me3SI. and Me3NCH2PhI in acetonitrile (molar ratios 2:1) yields (Me4N)4Sb8I28 (I), (Me3S)4Sb8I28 (2), and (Me3NCH2Ph)Sb2I7 (3), respectively. The struc­tures of 1-3 were determined from single crystal X-ray diffraction data. 1-3 crystallize in the monoclinic space group P21/n. 2: a = 1434.2(3). b = 1484.1(4). c = 2102.6(4) pm, β = 105.4(1)°, Z = 2. I: a = 1441.7(1). b = 1545.1(1). c = 2117.3(1) pm. β = 106.4(1)°, Z = 2. 3: a = 1004.4(1). b = 1378.8(1). c = 1899.3(2) pm. β = 94.2(1)°. Z = 4. The structures of I and 2 are very similar and consist of isolated cations and anions. The Sb8I28
4- ions of 1 and 2 and the anion of the same stoichiometry of (Ph4P)4Sb8I28 exhibit different struc­tures with a nearly identical Sb4I16 core. The anions of 3 are built up of polymeric cfiains.
Darstellung von Cyclopentadekaschwefel (S15) aus Titanocenpentasulfid und Sulfurylchlorid [1]
Authors: Strauss Reinhard , Steudel Ralf
Published: March 2015

Titanocene pentasulfide reacts with sulfuryl chloride under suitable conditions to give a mixture of mainly S10, S15, and S20 which can be separated by repeated crystallization and precipitation. Pure S15 is obtained as a lemon-yellow powder at low temperatures which transforms to a sticky mass at 20 °C. Solutions of S15 in CS2 are stable at 20 °C for months. Pure S15 does not decompose at 20 °C within a few hours. Raman spectra of S15 show stretching vibrations at 409-480 cm-1 and bending and torsional modes at < 270 cm-1.
Na5SnSb3 und K8SnSb4, zwei neue Zintlphasen mit tetraedrischen SnSb4-Baueinheiten
Authors: Eisenmann Brigitte , Klein Jürgen
Published: March 2015

The crystal structure of Na5SnSb3 (monoclinic, P21/c, a = 1859.4(6), b = 918.1(4), c = 1249.3(5) pm, β = 98.3°, Z = 8) contains SnSb4 tetrahedra which form chains by sharing common vertices. Isolated tetrahedral units SnSb4
8- are present in the crystal structure of K8SnSb4 (cubic, Fd3m, a = 1627.9(3) pm, Z = 8). The compounds are in agreement with the Zintl concept.
Kristallstrukturen von Octacyanomolybdaten(IV), I Ag4(NH3)5Mo(CN)8 · 1,5 H2O
Authors: Meske W. , Babel D.
Published: March 2015

The crystal structure of the triclinic compound Ag4(NH3)5Mo(CN)8- 1,5H2O could be refined in space group P1̄ (at T = 179 K: a = 974.6, b = 1477.6, C = 775.5 pm, α = 102.5, β = 94.6, y = 81.5°, Z = 2. Rg = 0.044 for 2744 independent reflections). The [Mo(CN)8]4_-groups form distorted square antiprisms with mean distances Mo-C = 215.7, C-N = 115.1 pm. They are connected to a puckered layer via four of their nitrogen ends which are tetrahedrally coordinated to silver (Ag-N = 226.7 pm). In between these layers and more or less tightly coordinated to their free cyano-N atoms dumbbells [CNAgNH3] and [Ag(NH3)2]+ are embedded. Their variation of distances and angles (Ag-N: 213 ... 216 pm, N-Ag-N: 150 ... 174°) is discussed.
Pseudohalogeno Metal Compounds, LXXI [1] Hexaazidoplumbate(IV). Crystal Structure of [AsPh4]2[Pb(N3)6]
Authors: Polborn Kurt , Leidl Erich , Beck Wolfgang
Published: March 2015

The crystal structure of [AsPh4]2[Pb(N3)6]2- has been determined by X-ray diffraction. The structure of [Pb(N3)6]2- (Ci symmetry) is analogous to that of [Sn(N3)6]2- with covalent Pb-N bonds (222-226 pm) and angles Pb-N-N between 115 and 121°. Irridiation (daylight) of [AsPh4]2[Pb(N3)6] in solution gives AsPh4[Pb(N3)3].
Zur Reaktion von [Cp2TiCl2] und [CpTiCl3] mit E(SiMe3)2 (E = S, Se) Die Kristallstrukturen von [Cp3Ti2S2Cl], [Cp4Ti2S2Cl2], [Cp3Ti2Se2Cl] und [Cp4Ti4Se7O] / Reaction of [Cp2TiCl2] and [CpTiCl3 ] with E(SiMe 3)2 (E = S. Se) The Crystal Structures of [Cp3Ti2S2Cl], [Cp3Ti2S2Cl2], [Cp3Ti2Se2Cl] and [Cp4Ti4Se7O]
Authors: Maué Paul G , Fenske Dieter
Published: March 2015

The reaction of [Cp2TiCl2 ] with E(SiMe3)2 leads to dinuclear Ti complexes. In [Cp3Ti2S2Cl] (1) and [Cp3Ti2Se2Cl] (3) two μ2 -S(Se) ligands bridge the Cp2Ti and CpTiCl units, respectively in contrast to these, [Cp4Ti2S2Cl2] (2) contains a μ2η1-S2 bridge connecting two Cp2TiCl fragments. A similar reaction of [CpTiCl3] with Se(SiMe3)2 leads to the tetranuclear cluster [Cp4Ti4Se7O] (4). 4 consists of a Ti4 -tetrahedron which encloses an oxygen atom.
[Na-15-Krone-5][MoF2Cl2(N3S2)]; Synthese und Kristallstruktur / [Na-15-Crown-5][MoF2Cl2(N3S2)]; Synthesis and Crystal Structure
Authors: Völp Karin , Baum Gerhard , Massa Werner , Dehnicke Kurt
Published: March 2015

The cyclothiazeno complex [Na-15-crown-5][MoF2Cl2(N3S2)] has been prepared by the reaction of sodium fluoride with [MoCl3(N3S2)]2 in acetonitrile solution in the presence of [15-crown-5]. The compound was characterized by its IR spectrum as well as by an X-ray structure determination (3560 observed independent reflexions, R = 0.039). Crystal data: monoclinic, P21/n, Z = 4; a = 1044.8(2); b = 1513.7(2); c = 1363.8(3) pm; β = 104.33(2)°. The structure consists of ion pairs, in which the sodium atom is seven-coordinated by the oxygen atoms of the crown ether molecule and by the two fluorine ligands of the [MoF2Cl2(N3S2)]- unit. The molybdenum atom is a member of the planar MoN3S2 ring; the fluorine atoms are coordinated in trans position to the nitrogen atoms of the cyclothiazeno ring.
Monoolefincobalt(0)-Komplexe / Monoolefincobalt(0) Complexes
Authors: Klein Hans-Friedrich , Lull Goetz , Rodenhäuser Birgit , Cordier Gerhard , Paulus Helmut
Published: March 2015

Mononuclear cobalt(o) complexes containing olefin and trimethylphosphane ligands Co(olefin)(PMe3)3 (olefin = C2H4 (1), C3H6 (2), cyclopentene (3), trans-1,2-diphenylethene (4), tetrafluorobenzo-bicyclo-(2.2.2)-octadiene (5)), are obtained from CoCl2 by reaction with magnesium in the presence of the ligands or by substitution of 3 with olefin. X-ray crystal structure determinations of 4 and 5 show a distorted tetrahedral arrangement of ligands around the cobalt atom. Chemical and spectroscopic properties are consistent with a paramagnetic valence state of the compounds in solution. By reaction with carbon monoxide a dicobalt complex is formed, while azobenzene gives paramagnetic Co(N2Ph2)(PMe3)2.
Darstellung und spektroskopische Charakterisierung von Fluor(trifluormethylsulfenyl)phosphonium-Salzen, CF3SPH2F+MF6
-(M = As, Sb) / Preparations and Spectroscopic Characterization of Fluoro(trifluoromethylsulfenyl)phosphonium Salts, CF3SPH2F+MF6
- (M = As, Sb)
Authors: Minkwitz Rolf , Liedtke Andreas
Published: March 2015

The preparations of the title compounds are reported. The species have been characterized by multinuclear (1H, 13C, 19F, 31P) NMR techniques. Their decomposition, leading mainly to PH2F2
+MF6-, was also studied. The Raman spectrum of CF3SPH2F+AsF6
- is presented.
Übergangsmetallketen-Verbindungen, XXXII [1] Darstellung kationischer η2 -Phosphinocarbenkomplexe durch Decarbonylierung von Wolframa-phospha-bicyclo[1.1.0]butanon-hexafluorophosphaten / Compounds of Transition Metal Ketenes, XXXII [1] Synthesis of Cationic η2 -Phosphinocarbene Complexes via Decarbonylation of Tungsta-phospha-bicyclo[l. 1.0]butanone Hexafluorophosphate Compounds
Authors: Kreißl F. R , Wolfgruber M
Published: March 2015

Mild thermolysis of cationic tungsta-phospha-bicyclo[1.1.0]butanone complexes yields novel η2 -phosphinocarbene complexes.
closo-Halogenohydrohexaborate, IV Protonierung, Deuterierung und Schwingungsspektren von claso-Hexaboraten / closo-Halogenohydrohexaborate, IV Protonation, Deuteration and Vibrational Spectra of closo-Hexaborates
Authors: Preetz W , Heinrich A , Thesing J
Published: March 2015

The weak Brönsted acids B6H7
- and XB6H6
-, X = Cl, Br, I; pka : 7-4,75, are formed by protonation of B6H6
2- and XB6H5
2- respectively. The deuteration rates, evaluated from integrated IR band intensities of the BH and BD stretching vibrations, are linearly dependent on the mole fractions of the protonated species, and decrease with increasing degree of halogenation in the series Cl>Br>I. H atoms trans-positioned to halogens are exchanged 100 times more rapidly than the remaining ones. The activation energy for the H/D exchange amounts to 76 ± 1,5 kJ/mol for B6H7
-. The lower symmetry of the protonated borates is evident from additional IR and Raman bands. They are distinguished from the corresponding Brönsted bases by a high frequency shift of the BH stretching vibrations in the order of 100 cm-1. Due to the pH dependent equilibrium B6H6
2-/B6H7
- and different solubilities of the tetrabutylammonium salts, the separation of B6H6
2-/B12H12
2- mixtures is achievable. In alkaline solutions the very soluble B6H6
2- is present, whereas (TBA)2B12H12 precipitates quantitatively. By subsequent cautious acidification of the supernatant, insoluble (TBA)B6H7 is obtained.
Biocatalytical Transformations, III [1] Regioselective Enzymic Deacetylations of Laevoglucosane Triacetate
Authors: Csuk René , Glänzer Brigitte I
Published: March 2015

Several hydrolytic enzymes (porcine liver esterase, lipase from wheat germ type I, and the lipase from rhizopus javanicus) efficiently deacetylate laevoglucosane triacetate (2) with good regioselectivity into diacetylated laevoglucosane derivatives (3-5).
Synthese und Kristallstruktur von [(C6Et6)(C6H5Me)GaGaCl4]· 1/2 (C6Et6): Ein gemischter Bis(η6-aren)gallium(I)-Komplex / Synthesis and Crystal Structure of [(C6Et6)(C6H5Me)GaGaCl4] · 1/2 (C6Et6): A Mixed Bis(η6-arene)gallium(I) Complex
Authors: Schmidbaur H. , Nowak R. , Müller G.
Published: March 2015

Crystals obtained from solutions of hexaethylbenzene and anhydrous Ga[GaCl4] in toluene on cooling have the stoichiometry [(C6Et6)(C6H5Me)GaGaCl4] · 1/2 C6Et6. a = 9.760(1), b = 21.447(2), c = 17.754(2) Å. β = 95.47(1)°; monoclinic. space group P21/n. Z = 4.

Each Ga(I) center is η6-bonded to one molecule of hexaethylbenzene and to one molecule of toluene. The two rings form an angle of 38,8°. The remaining crystal hexaethylbenzene is situated between two complex units, which are related by an inversion center located in the center of the ring.
Neue Übergangsmetallkomplexe mit dem Ph2S=N-Liganden / New Transition Metal Complexes with the Ligand Ph2S=N
Authors: Roesky Herbert W. , Zimmer Michael , Schmidt Hans Georg , Noltemeyer Mathias
Published: March 2015

S,S-Diphenyl-N-(trimethylsilyl)sulfimine (1) reacts in a molar ratio of 1:1 with V(O)Cl3 , V(O)F3 , NbCl5, MoCl5 and FeCl3 to yield Ph2S=NV(O)Cl2 (2). Ph2S=NV(O)F2 (3). Ph2S=NNbCl4 · CH3CN (4), Ph2S=NMoCl4·CH3CN (5). and (Ph2S=NFeCl2)2 (6), respectively. The crystal structures of 2 and (dimeric) 6 are reported.
Reaktionen von Titantetrachlorid mit Bistrimethylsilylsulfid. Die Kristallstrukturen von (NEt4)2[TiSCl4], (PPh4)2[TiSCl4]·2CH2Cl2, (PPh4)2[Ti3O(S2)3Cl6]CH3CN und Ti4O(S2)4Cl6 / Reactions of Titanium Tetrachloride with Bistrimethylsilyl Sulfide. Crystal Structures of (NEt4)2[TiSCl4], (PPh4)2[TiSCl4]·2CH2Cl2, (PPh4)2[Ti3O(S2)3Cl6]CH3CN and Ti4O(S2)4Cl6
Authors: Krug Volker , Koellner Gertraud , Müller Ulrich
Published: March 2015

The reaction of TiCl4 with (Me3Si)2S in dichloromethane yields black, insoluble, impure TiSCl2. In the presence of oxygen, additionally Ti3O(S2)3Cl4 and Ti4O(S2)4Cl6 are formed. By reactions of TiSCl2 with NEt4Cl and PPh4Cl in dichloromethane (NEt4)2[TiSCl2] and (PPh4)2[TiSCl4] ·2CH2Cl2 are formed, respectively. They were characterized by their IR spectra and by X-ray crystal structure determinations. They contain the square-pyramidal [TiSCl4]2- ion. which has a rather short Ti = S bond of 211.1(2) pm. Crystal data: (NEt4)2[TiSCl4]: tetragonal. P4/n, a = 923.9(3). c = 1406.7(2) pm. Z = 2. 966 unique observed reflexions. R = 0.053; positionally disordered ethyl groups. (PPh4)2[TiSCl4] · 2CH2Cl2: triclinic, P1, a = 1009.7(4), b = 1115.1(3). c = 1242.1(5) pm, α = 70.27(3), β = 79.06(3), γ = 81.37(3)°, Z = 1, 1504 reflexions, β-(AsPh4)2UCl6·2CH2Cl2 structure type, high R = 0.107 due to positional disorder of the anion. Addition of NEt4Cl or PPh4Cl in CH2Cl2 to the primary reaction product in presence of O2 yields (NEt4)2[Ti3O(S2)3Cl6] and (PPh4)2[Ti,O(S2)3Cl6] · CH2Cl2, respectively. Upon recrystallization of the latter from acetonitrile, (PPh4)2[Ti3O(S2)3Cl6] · CH3CN is obtained which forms triclinic crystals with a = 1138.8(3). b = 1268.8(4), c = 2166.4(6) pm, α = 101.26(3). β = 97.21(2). γ = 109.24(2)°, Z = 2, P1 (3053 reflexions, R = 0.070). The [Ti3O(S2)3Cl6]2- ion has a cluster-like structure with Ti atoms at the vertices of a triangle, with a μ3-O bridging atom and with tree bridging disulfide groups. Crystal data for Ti4O(S2)4Cl6: monoclinic, C2/c, a - 917.3(2), b - 1632.5(2), c = 1268.5(2) pm, β - 108.35(2)°, Z = 4. 1009 reflexions. R = 0.027. In the Ti4O(S2)4Cl6 molecule, four Ti atoms form a distorted tetrahedron around an μ4-O atom; two edges of the tetrahedron are spanned by chloro bridges, four edges by disulfide bridges.
Synthese und Eigenschaften einiger neuer Organoindium-Methylenstannyl-Verbindungen / Preparation and Properties of Some New Organoindium Methylenestannyl Compounds
Authors: Schumann Herbert , Mohtachemi Reza , Schwichtenberg Michael
Published: March 2015

Me2Sn(CH2Li)2 reacts with Me2InCl or (Me2NCH2CH2O)2 InCl with formation of the new compounds Me2Sn(CH2InMe2)2 or Me2Sn(CH2In(OCH2CH2NMe2)2)2 . The compounds are characterized by elemental analyses, 1H, 13C, 119Sn NMR and IR spectra.
Rhodium-zentrierte Bildung eines Cyclobutenyl-Liganden und Umlagerung in einen Cyclopentadienyl-Komplex / Rhodium-centered Formation of a Cyclobutenyl Ligand and Rearrangement to a Cyclopentadienyl Complex
Authors: Müller Jörn , Tschampel Matthias , Krüger Carl
Published: March 2015

Cyclization of two diphenylacetylene molecules occurs if [(cod)RhCl] 2 (cod = 1.5-cyclooc-tadiene) is treated with methyllithium in the presence of tolane. The isolated (cod)Rh complex 2 contains an exo-methyl-tetraphenylcyclobutenyl ligand and was characterized by X-ray diffraction analysis. Thermolysis of 2 in acetonitrile causes ring expansion of the methylcyclobutenyl unit with formation of the tretraphenylcyclopentadienyl complex 3 together with 3-methyl-tet-raphenylcyclobutene. Mechanistic aspects are discussed as well as spectroscopic data of the new compounds.
Polysulfonylamine, XIII [1] N-Acylonium-Salze des Dimesylamins: Synthese und Massenspektren / Polysulfonylamines, XIII [1] N-Acylonium Salts of Dimesylamine: Synthesis and Mass Spectra
Authors: Blaschette Armand , Linoh Karin , Safari Firouz
Published: March 2015

N-Acyl dimesylamines. like acyl chlorides, react with 4-dimethylaminopyridine and other tertiary nitrogen bases to give either solid N-acylonium dimesylaminides (1-3). or onium dimesylaminides (e.g. 4) originating from ketene elimination (eq. (5)). The expected acyl transfer properties of N-acylonium dimesylaminides are confirmed by reactions of l a with phenol, 4-nitrophenol, p-thiocresol, and N-methylaniline, and of 1b with phenol, resulting in 0-. S-. or N-acylation, respectively. With exception of compounds 1b and 3, all dimesylaminides could be characterized by their cation and anion mass spectra using field desorption, secondary ion mass spectrometry or fast atom bombardment
Die Struktur von [(tert-C4H9)3PI][W(CO)4l3] — ein Beitrag zur Diskussion des Akzeptorverhaltens von Iodphosphoniumionen/ The Structure of [(tert-C4H9)3PI][W(CO)4l3] — a Contribution on the Acceptor Properties of Iodophosphonium Ions
Authors: Kuhn Norbert , Ralf Jüschke , Mont Wolf-Walther du , Bätcher Michael , Bläser Dieter , Boese Roland
Published: March 2015

(2)

The structure of [t-Bu3PI][W(CO)4I3] has been determined by X-ray diffraction. The anion of 2 consists of a CO-capped distorted octahedron. One iodine atom of the anion acts as donor towards the iodophosphonium cation. In 2 the I···I interaction is weaker and the P-I bond is stronger than in t-Bu3PI2. Structural features of t-Bu3PI⊕ cations are compared with those of the isoelectronic molecule t-Bu3P = Te.
Zur Photoionisation und Ionenfragmentation von SF4/Photoionization and Ion Fragmentation of SF4
Authors: Jochims H.-W. , Rühl E. , Baumgärtel H.
Published: March 2015

The ionization potentials of sulfurtetrafluoride have been measured using threshold photoelectron spectroscopy and com pared with theoretical calculations. The decay of SF4
+ has been studied by photoionization mass spectrometry and photoion-photoelectron coincidence. The break-down graphs reveal competing decay processes. Bond dissociation energies in SF4
+ have been calculated.
Photoionenspektroskopie an Schwefelchloridpentafluorid SF5Cl, das Ionisationspotential von Schwefelpentafluorid SF5/Photoion Spectroscopy of Sulfurchloridepentafluoride SF5Cl, the Ionization Potential of Sulfurpentafluoride SF5
Authors: Baumgärtel H. , Jochims H .-W. , Rühl E. , Lösking O. , Willner H.
Published: March 2015

The appearance potentials of fragment ions from SF5Cl have been measured in the energy range 12 - 20 eV by means of photoionization mass spectrometry. From these data, the ionization potential of SF5 comes to 9.65 eV.
Dithiocarbimates from Sulfonamides, Part 2: Preparation and X-Ray Crystal Structures o f (PPh4)2[Ni(S2C = N —S 0 2—Ph)2] and (PPh4)2[Ni(S2C = N —S 0 2—C6H4—CI)2] * 2 H20
Authors: Hummel Hans-Ulrich , Korn Uwe
Published: March 2015

By reaction of K2[S2CNSO2C6H5] · 2H2O and K2[S2CNSO2C6H4Cl] · 2H2O, respectively, with Ni(CH3COO)2 · 4H2O the complex anions [Ni(S2C = N-(SO2-C6H5)2]2- and [Ni(S2C = N-SO2-C6H4-Cl)2]2- are formed and have been isolated in form of their (PPh4) salts. (PPh4)2[Ni(S2C = N-SO2-Ph)2] crystallizes monoclinicly. space group P21/a with a = 19.081(4), b = 9.106(1), c = 17.630(4) Å and β = 113.42(6)° with Z = 2. (PPh4)2[Ni(S2C = N-SO2-C6H4-Cl)2] · 2H2O crystallizes triclinicly, and the non-standard setting Cl has been choosen with a = 15.732(3), b = 22.509(4), c = 9.521(1) Å , ɑ = 96.30(6), β = 117.57(9), γ = 88.93(5)° and Z = 2. Within the complex anions nickel has the site-symmetry 1 and is coordinated by four sulfur atoms with Ni-S mean = 2.198 Å. The Ni(S2C = N-SO)2 units are essentially planar in both systems. This planarity gives rise to conjugation effects involving the SO2 group and the π-system of S2C = N - as well as the lone pair on N.
13C- und 15N-NMR-spektroskopische Untersuchungen einiger Pentacarbonylchrom-Aminophosphan-Komplexe/13C and 15N NMR Spectroscopic Study of Some Pentacarbonylchromium-Aminophosphane Complexes
Authors: Wrackmeyer Bernd , Schamei Klaus , Herberhold Max
Published: March 2015

13C and 15N NMR data are reported for the free aminophosphanes ʹBu3-nP(NH2)n (n = 1 (1), 2 (2)), for the corresponding pentacarbonylchromium complexes (OC)5Cr-P(ʹBu)3-n(NH2)n (n = 1 (3), n = 2 (4), n = 3 (5)), and for other (OC)5Cr-aminophosphane complexes such as (OC)5Cr-P(NMe2)3, (6 ) and a binuclear complex (7) in which the sulfurdiimide derivative ʹBu(NH2)P-NSN-P(NH2)ʹBu serves as the phosphane ligand. Various techniques (e.g. INEPT and reverse two-dimensional (2D) 1H {15N}-experiments) have been used for recarding the 15N NMR spectra at natural abundance. In contrast to suggestions in the literature, the relationship between the 13C NMR parameters for the axial and equatorial CO groups and the σ-donor/π-acceptor properties of the phosphane ligand is not straightforward. The 15N resonances of the (OC)5Cr complexes 3, 4, 6 are shifted to higher frequencies with respect to those of the free ligands, and there is a regular decrease in 15N nuclear shielding in the series of 3, 4, 5. The |1J(31P15N)| values vary between 17 and 65 Hz, the smaller values being observed for the (OC)5Cr complexes. The lack of a regular change in the magnitude of 1J(31P15N) in the series 3, 4, 5 indicates that this parameter is influenced by the nature of both the Cr-P and the P-N bonds as a function of the number of amino groups.
Schwingungsspektren der Clusterverbindung Nb6F15/Vibrational Spectrum of the Cluster Compound Nb6F15
Authors: Kliche G. , Schnering H. G. von
Published: March 2015

Infrared and Raman spectra of the metal cluster compound [Nb6F12]F3 (cubic Im3̄m; Z = 2) are reported. The three intense m odes observed in the Raman spectrum at 215. 267, and 337 cm-1 and a weak mode observed in the infrared spectrum at 287 cm-1 are assigned to the T2g, Eg, A1g, and T1u vibrational modes of the Nb6 octahedra. The assignment is supported by normal coordinate analysis and Raman measurements at 47 kbar. The valence force constants are f(Nb-Fi) = 2.04, f(Nb-Fa-a) = 1.30 and f(Nb-Nb) = 0.97 N cm-1 metal-to-metal interaction in the cluster.
Chemie an starren Grenzflächen, 9 [1]. Eigenschaften und Verhalten Oniumgruppen-modifizierter Aerosile Einige Beispiele interpartikulärer Reaktionen/Chemistry on Rigid Interfaces, 9 [1]. Properties and Behaviour of Onium Group Modified Aerosils Some Examples of Interparticular Reactions
Authors: Hornera L. , Rothb W.
Published: March 2015

Aerosils, Onium Groups. Interparticular "cross-linking" Aerosils with covalently linked onium group 2a-f catalyze the exchange of halogene (Finkel-stein-Reaction) and migrate in an electric field depending on the nature of the end groups and the kind of the suspension medium.

Electroactive groups covalently linked with aerosil are electroreduced on mercury and lead cathodes. The possibility of an interparticular cross linking is demonstrated.
The Synthesis of Some Cyclopentadienyliron-Indium Complexes
Authors: Norman Nicholas C.
Published: March 2015

Treatment of indium trichloride with three equivalents of the cyclopentadienyliron carbonyl anions, [Fe(CO)2(η-C5H4R)]- (R = H, Me) affords the tri-iron indium complexes [In {Fe(CO)2(η-C5H4R)}3] (R = H, Me) as dark red crystalline materials. Both compounds were characterized by spectroscopic and analytical methods. Infrared spectroscopy indicates that both complexes are undissociated in solution in contrast to previously reported analogous molybdenum containing species.
Synthese und Struktur von trimerem 1,5-Bis(p-ethoxyphenyl)pentaazadienidokupfer(I) — ein Komplex mit kurzen Cu—Cu-Kontakten in einer linearen Cu3
3+-Einheit / Synthesis and Structure of Trimeric 1,5-Bis(p-ethoxyphenyl)pentaazadienido-copper(I) — A Complex with Short Cu —Cu Contacts in a Linear Cu3
3+ Unit
Authors: Schmid Raimund , Strähle Joachim
Published: March 2015

From a saturated solution of EtOC6H4N2NHN2C6H4OEt in aqueous ammonia and Cu(NH3)4
2+ dark brown Cu(EtOC6H4N5C6H4OEt)2 (1) is obtained as an explosive precipitate. Upon heating in pyridine 1 is reduced to trimeric 1,5-bis(p-ethoxyphenyl)pentaazadienido copper(I) (2). 2 forms air-stable red crystals with the rhombohedral space group R3̄̄ and the lattice constants a = 1371.2(4) pm, α = 86.88(3)° and Z = 2. In 2 a linear Cu3
3+ chain is coordinated by the atoms N 1, N 3 and N 5 of three pentaazadienido ligands, such that each Cu atom obtains a trigonal planar coordination by three N atoms.

As 2 is located on the threefold axis of the space group R3̄̄, it has the Symmetrie C3. The distances Cu 2-N 3 = 192.7 pm to the more basic central atoms N 3 are shorter than the distances Cu 1-N 1 = 205.7 and Cu 3-N 5 = 201.5 pm to the outer N atoms of the N5 chains. The pentaazadienido ligand forms a planar N5 zig-zag chain with distances in the range of 127.8 to 135.4 pm. The very short Cu-Cu distances of 234.8 and 236.1 pm can be explained by bonding interactions between the d10 centers.
Die Kristallstruktur von [Ca(N3)2(H2O)2] · C6H14N4 bei 100 K /The Crystal Structure of [Ca(N3)2(H2O)2] · C6H14N4 at 100 K
Authors: Mautner Franz A. , Krischner Harald , Kratky Christoph
Published: March 2015

Abstract The crystal structure of calcium azide dihydrate trans-bicyclo-[4.4.0]-1,4,6.9-tetraazadecane has been determined by single crystal X-ray diffraction at 100 K. [Ca(N3)2(H2O)2 (C6H14N4 crystallizes in the orthorhombic space group Pnma, Z = 4. with a - 1396.6(5), b = 1407.1(5), c = 712.2(2) pm. Calcium is hexacoordinated to four azide groups and two water molecules. The elongated octahedra are linked via μ(1,3)-bridging azide ions to form monolayers parallel to the ac-plane. The C6H14N4 molecules are arranged between these layers.
Photoredox Reactions of Hg(CN)2/[Fe(CN)6]4- and [HgCo2(CN)10]6- Induced by Inner-Sphere Metal to Metal Charge Transfer Excitation
Authors: Kunkely H. , Stochel G. , Vogler A.
Published: March 2015

Abstract Incomplexes of the type [(NC)2HgIIN CFeII(CN)5]4- which are formed in aqueous mixtures of Hg(CN)2 and [Fe(CN)6]4- both metals are weakly coupled. Optical metal to metal charge transfer (MMCT) excitation from FeII to HgIIleads to the reduction of HgII to Hg0 an the oxidation of [Fe(CN)6]4- to [Fe(CN)6]3-. In the complex [(NC)5CoI-HgII-CoI(CN)5]6- the m etals are strongly coupled by direct but polar metal metal bonds. MMCT (CoI ￫ HgII) excitation induces the photoredox reaction: [HgCo2(CN)10]6-￫Hg0 + 2[Co(CN)5]3-.
Synthese und Kristallstruktur des Amidinatokomplexes Ph-C(NSiMe3)2TeCl3 / Synthesis and Crystal Structure of the Amidinato Complex Ph —C(NSiMe3)2TeCl3
Authors: Hey Evamarie , Ergezinger Christina , Dehnicke Kurt
Published: March 2015

Abstract The title com pound has been prepared by the reaction o f N ,N ,N '-tris(trimethylsilyl)-benzamidine with tellurium tetrachloride in CH2Cl2 solution. The complex was characterized by an X-ray structure determination. Crystal data: space group P 1̄ , Z = 2, (2428 observed independent reflexions, R = 0.031). Lattice dimensions (19 °C): a = 946.7(1), b = 1031.5(1), c = 1337.1(1) pm; α = 67.411(8)°, β = 68.508(9)°, γ = 67.195(8)°. Ph-C(NSiMe3)2TeCl3 forms monomeric molecules, in which the tellurium atom is ϕ-octahedrally surrounded by three chlorine atoms and by the two nitrogen atoms of the amidinato chelate (bond lengths Te -N = 209.6 and 219.2 pm). The lone pair at the tellurium (IV) center and the small bite angle of the ligand cause a strong distortion of the octahedral geometry.
Iminiumtetrachloroaluminate als leistungsfähige Mannich-Reagenzien. α-Aminoalkylierung von Enaminen / α-Aminoalkylation of Enamines with Iminiumtetrachloro-aluminates
Authors: Risch Nikolaus , Esser Achim
Published: March 2015

Abstract We report the use of iminiumtetrachloro-aluminates 1a , 2a, and 3a in Mannich reactions. These salts are easily synthesized and offer some important advantages compared to iminium salts 1 b -e.
Synthesis of 1-Benzoylpyrroline Derivative and Related Compounds
Authors: Elbannany Afaf A. A. , Ibrahim Laila I.
Published: March 2015

Several new pyrroline derivatives were prepared from 4-amino-1-benzoyl-3-benzylidene-4-pyrroline- 2-one (4).
π-Olefin-Iridium-Komplexe, XV [1] Kationische Bis(2.3-dimethylbutadien)iridium-L-Verbindungen mit verschiedenen Donorliganden L/π-Olefin Iridium Complexes, XV [1] Cationic Bis(2.3-dimethylbutadiene)iridium-L Compounds with Various Donor Ligands L
Authors: Müller Jörn , Hänsch Corinna , Pickardt Joachim
Published: March 2015

(dmb)2IrCH3 (dmb = 2.3-dimethylbuta-1.3-diene) reacts with Ph3CBF4 in CH2Cl2 to form the cation [(dmb)2Ir]+ which crystallizes as the adduct [(dmb)2Ir(OCMe2)]BF4 from acetone solution. The labile acetone ligand is easily displaced by pyridine, cyclohexylisonitrile, phosphane and arsane donor molecules. X-ray diffraction analysis of [(dmb)2Ir(AsPh3)]BF4 reveals tetragonal pyramidal coordination at the iridium atom with the arsane ligand in axial position and with isolated BF4 anions. Spectroscopic data of the new [(dmb)2IrL]BF4 compounds are discussed and related with metal-ligand bond interactions.
Dynamisches Verhalten dimerer 1,3,2,4λ2-Diazasilastannetidine und -plumbetidine in Lösung — eine Multikern-NMR-Studie/Dynamic Behaviour of Dimeric 1,2,3,4λ2-Diazasilastannetidines and -plumbetidines in Solution — a Multinuclear NMR Study
Authors: Wrackmeyer Bernd , Horchler Klaus , Zhou Hong , Veith Michael
Published: March 2015

1,3-Diisopropyl-2,2-dimethyl-1,3,2,4λ2-diazasilastannetidine (1b) and -plumbetidine (2b) are dimeric [(1b)2, (2b)2] in solution. At room temperature the structure of (1b)2 is fluxional. The dynamic behaviour is interpreted - on the basis of 1H. 13C, 29Si and 119Sn NMR data - as an intramolecular process in which the four-membered rings keep their identity. Such a process involves either concerted opening of the two coordinative Sn - N bonds and mutual slippage of the two rings, or consecutive cleavage of one of the coordinative Sn - N bonds and rotation about the other one. At room temperature the dimer (2b)2 is in equilibrium with its monomer 2b, whereas at low temperature the dynamic process corresponds to that established for (1b)2. In solutions which contain a mixture of the dimers (1b)2 and (2b)2, the presence of the mixed dimer 1b/2b can be proved unambiguously by consistent 29Si, 119Sn and 207Pb NMR data.
Donor/Akzeptor-Komplexe aus 1,3,5-Tris(dimethylamino)benzol und 1,2,3,4,5,6-Hexacyanobenzol/Donor/Acceptor Complexes from 1,3,5-Tris(dimethylamino)benzene with 1,2,3,4,5,6-Hexacyanobenzene
Authors: Keller  , Niebl R. , Renner G. , Ruhr D. von der , Kilic A. K. , Schweitzer D.
Published: March 2015

Reaction of 1,3,5-tris(dimethylamino)benzene (TDMAB ) with 1,2,3,4,5,6-hexacyanobenzene (HCNB) in acetonitrile solution gives - depending on the crystallization method - two different products: dark needles of a 1:1 (1) and black compact crystals with a metallic lustre of a 2:1 (2) charge transfer complex. 2 crystallizes in the triclinic space group P1 , Z = 1, a = 9.9489(22), b = 10.0555(21), c = 10.1418(20) Å , α = 115.006(16)°, β = 102.820(17)°, γ = 93.647(18)°, V = 882.3 Å3, dc = 1.2 g cm-3, measured at room temperature, R = 0.053 for 2670 observed independent reflections and 301 parameters. The structure contains isolated “trimers” of one HCNB acceptor which is “pancaked” by two TDMAB neighbors. The arrangement of these trimers in the lattice results in alternating HCNB and TDMAB sheets. The solid is diamagnetic.

1 could not be obtained in crystals suitable for a single crystal X-ray investigation. Its paramagnetism which is observed immediately after preparation disappears in the course of several days.
Neue Juglomycine/New Juglomycins
Authors: Lessmann Holger , Krupa Johann , Lackner Helmut , Jones Peter G.
Published: March 2015

A presumed precursor of the juglomycins, (2S, 3'R, 4'R)-2,3-dihydro-juglomycin A (3), has been isolated and its X-ray structure determined. 3 forms an equilibrium with a novel hemi-ketal (4). The structures of new juglomycins (C, D, E, F) and some derivatives have been elucidated and their structure/activity-relationships are discussed.
Zwei-und dreikernige Fluorooxoanionen des Vanadins. Kristallstrukturen von Cs(NMe4)[V2O2F8(H2O)] und (Na,K)(NMe4)2[V3O3F12] / Di- and Trinuclear Fluorooxoanions of Vanadium. Crystal Structures of Cs(NMe4)[VO2F8(H2O)] and (Na,K)(NMe4)2[V3O3F12]
Authors: Hilbers Martin , Leimkühler Manfred , Mattes Rainer
Published: March 2015

From aqueous HF solutions the following fluorooxo complexes have been crystallized and characterized: AI(NMe4)2[V3O3F12] (1), AI = Na. K; K2(NMe4)[V2O2F9]·H2O (2); Cs(NMe4)[V2O2F8(H2O)] (3) and NMe4[VOF4] (4). The structures of 1 and 3 have been determined.

Crystal data: 1c, hexagonal, space group P63/m . a = 1695.0(9), c = 1248.1(5) pm. Z = 6: 1803 reflections. R = 0.045. 3, orthorhombic. space group Pnma, a = 2152.8(7), b = 751.5(2), c = 850.7(2) pm, Z = 4; 1379 reflections, R = 0.030. 1 contains a trimeric, cyclic anion with asymmetrically bonded μ-fluoroligands and terminal V = O groups in the same plane; the anion of 3 is a fluorobridged dimer with unequally coordinated vanadium atoms with terminal V = O groups. The preparation of these com pounds establishes the presence of VOF4(H2O)- species in aqueous solutions.
Röntgenographische und spektroskopische Untersuchung einiger Strontium-und Zink-substituierten Calcium-Fluorapatite / X-Ray and Spectroscopic Investigation of Some Strontium and Zinc Substituted Calcium Fluoroapatites
Authors: Apella M. C. , Tuttolomondo M. E. , Baran E. J.
Published: March 2015

Simultaneous strontium and zinc substitution for calcium in the fluoroapatite lattice was investigated. Crystallographic data for different members of the series Cain10-x-ySrxZny(PO4)6F2 were obtained from X-ray powder diagrams. The effects of the substitutional process on the strength of the phosphate P -O-bonds were checked by Raman spectroscopy. For comparative purposes, the first members of the series Sr10-xZx(PO4)6F2 were also investigated in a similar way.
Darstellung und Schwingungsspektren von Fluoro-Chloro- Platinaten(IV) einschließlich der Stereoisomeren / Preparation and Vibrational Spectra of Fluoro-Chloro-Platinates(IV) Including Stereoisomers
Authors: Preetz W. , Erlhöfer P.
Published: March 2015

The reaction of [PtCI6]2- with BrF3 generates the mixed complexes [PtFnC6-n]2- , n = 1- 5, of which the species with n = 2. 3, 4 are cis-configurated. Due to the stronger trans-effect of Cl compared to F, on treatment of [PtF5Cl]2- and cis-[PtF4Cl2]2- with Cl- the trans-isomers are formed stereospecifically. The pure fluoro-chloro-platinates(IV) are separated by ion exchange chromatography on diethylaminoethyl-cellulose. The vibrational spectra o f the mixed ligand complexes are completely assigned according to point groups D4h, C4v, C3v and C2v. The Pt-Cl stretching vibrations of [PtF5Cl]2-, trans-[PtF4Cl2]2-, mer-[PtF3Cl3]2- and [PtFCl5]2- are split by the isotopes 35Cl and 37Cl, showing well resolved sharp Raman lines in the expected ratio of intensities.
Heterocyclic Synthesis with Nitriles: A Novel Synthesis of Some Thiophene and Thieno[2,3-d]pyrimidine Derivatives, II [1]
Authors: Abdelrazek Fathy Mohamed
Published: March 2015

Some differently substituted 4-phenylthiophene derivatives 2a-d and 8a, b have been prepared from α-substituted-β-thiocyanatomethyl cinnamonitrile (1). The thiophene derivatives 2a, b and 8a react with trichloroacetonitrile and formamide to afford thieno[2,3-d]pyrimidine derivatives 4, 5 a-c, 7 and 9 a-c, respectively.
Synthesis and Reactivity of Copper(II) Complexes with New Binucleating Ligands Derived from 16-or 20-Membered N4-Macrocycles
Authors: Nishida Yuzo
Published: March 2015

New binucleating ligands, (L1) N ,N′,N″,N‴-tetrakis(2-benzimidazolylmethyl)-1,4,9,12-tetra-azacyclohexadecane, and (L2) N ,N′,N″,N‴-tetrakis(2-benzimidazolylmethyl)-1,4,11,14-tetra-azacycloeicosane were prepared. From the reaction mixture of copper(II) salt and the ligand, new binuclear copper(II) complexes, Cu2(L1) (NO3)4 (1), Cu2(L2)(NO3)4 (2), Cu2(L2)Br4 (3), and trinuclear complexes, Cu3(L1)Cl6 (4), and Cu3(L2)Cl6 (5) were obtained. Cyclic voltammograms revealed that the trinuclear complexes 4 and 5 are composed with the binuclear complex (1 or 2) and [CuCl4]2-. The interaction between two metal ions in the binuclear complexes are confirmed on the basis of the ESR spectra. These binuclear complexes exhibit higher catalytic activity for the oxidation of TMPD by O2 molecule than those of structurally rigid binuclear copper(II) complexes and of flexible binuclear complexes in which two copper(II) coordination sites are linked by a single polyatomic chain.
Die Phasendiagramme der Systeme Dimethyldichlorsilan mit 2.4-Lutidin und 2.6-Lutidin/Phase Diagrams of Dimethyldichlorosilane with 2.4-Lutidine and 2.6-Lutidine
Authors: Hensen Karl , Dräbing Michael
Published: March 2015

A phase equilibrium study of the systems

dimethyldichlorosilane with 2.4-lutidine and

2.6-lutidine is presented with evidence for the

existence of the incongruently melting compounds

2.6-lutidine · Me2SiCl2, (2.6-lutidine)2 · Me2SiCl2

and the congruently melting compound

2.4-lutidine · Me2SiCl2.