bluuebunny/crossref_metadata_2025 huggingface dataset:
Polychlorinated Biaryl Heterocycles as Potential Ligands. Reactions between Octachloro-1,10-phenanthroline and -2,2′-bipyridine with Copper(I) and Other Metal Ions
Authors: Titze Christoph , Kaim Wolfgang
Published: February 2015

Perchlorinated derivatives of the common o-diimine chelate ligands 2,2′-bipyridine and 1,10- phenanthroline were synthesized and tested for their coordination behavior towards metal ions. Octachloro-1,10-phenanthroline (ocp) was obtained via chlorination with PCl5 under pressure (300°C, 18 h). It fails to form stable complexes with e.g. Fe2+, Mn2+, Ru2+, Ni2+. Zn2+ or Cd2+, but yields complex cations [M(ocp)2]+ with M = Cu, Ag. The crystal structure analy­sis of the red tetrafluoroborate of the copper(I) complex cation reveals a distorted tetrahedral coordination at the metal with a slight tendency towards the trigonal-pyramidal arrangement; two essentially planar ligands with small bite angles intersect at almost right angle. Relative to conventional bis(1,10-phenanthroline)copper(I) complexes with similar structures. [Cu(ocp)2]+ has oxidation and reduction potentials shifted positively by about 1 V which leaves the energy of the main MLCT absorption features little changed. Attempts to synthesize RuCl2(ocp)2 in DMF produced as substituted product a symmetrical bis(dimethylamino)-hexachloro-1,10-phenanthroline which can be oxidized electrochemically in two steps. In contrast to ocp, octachloro-2,2′-bipyridine (ocb) showed no detectable complexation with Cu+ and a very neg­ative reduction potential, most probably due to its inability to exhibit a low-energy coplanar conformation.
Untersuchungen an Polyhalogeniden, XXV [1]. Triiodide von Pyridinkomplexen des zweiwertigen Palladiums: Dipyridinpalladiumhexaiodid Pd(py)2I6 und zwei Formen des Tetrapyridinpalladiumhexaiodids Pd(py)4I6 / Studies on Polyhalides, XXV [1]. Triiodides of Pyridine Complexes of Divalent Palladium: Di(pyridine)palladium Hexaiodide Pd(py)2I6 and Two Forms of Tetra(pyridine)palladium Hexaiodide Pd(py)4I6
Authors: Tebbe Karl-Friedrich , Gräfe-Kavoosian Arista , Freckmann Bernhard
Published: February 2015

Two forms of the new compound Pd(py)4I6 have been prepared by the reaction of stoichiome­tric amounts of PdCl2, C5H5N, KI and I2 in water. One modification crystallizes triclinically in space group Ρ1̄ with a = 907.7(3), b = 960.5(7), c = 992.0(4) pm, α = 117.31 (4), β = 103.35(3), γ = 86.01(5)° and Z = 1, the other orthorhombically in space group Pnnm with a = 891.6(4), b = 1047.6(4), c = 1659.1(5) pm and Z = 2. Both structures may be described as layerlike packings of I3
- anions and [Pd(py)4]2+ cations. Differences arise from the orientations of the anions and cations within these layers.

The new compond Pd(py)2l6 has been prepared by recrystallisation of Pd(py)4I6 from chlo­roform. It crystallizes in the monoclinic space group I2/a with a = 1801.1(4), b = 584.0(1), c = 2220.5(6) pm, β = 115.78(2)° and Z = 2. The structure is built up from quasi square planar complexes [Pd(py)2l2] and iodine molecules I2 linked together to give alternating screw- and zigzag-shaped chains ^[I_-I2] along [1 0 01 forming nets of type (10, 3) including the Pd2+ ions. The structure may also be described as a layerlike packing of the anionic chains 1
∞[I- · I2] and linear complex cations [Pd(py)2]2+ parallel [0 1 1].
Untersuchungen an Polypseudohalogeniden, VII [1]Darstellung und Kristallstruktur des [K(Crypt-2.2.2)] I(ICN)2 / Studies on Polypseudohalides, VII [1] Preparation and Crystal Structure of [K(Crypt-2.2.2)] I(ICN)2
Authors: Tebbe Karl-Friedrich , Gräfe-Kavoosian Arista
Published: February 2015

The new compound [K(Crypt-2.2.2)]I(ICN)2 has been prepared by the reaction of [K(Crypt- 2.2.2)]I with excess ICN in Ethanol. It crystallizes in the triclinic space group Ρ1̄ with a = I 192.3(2), b = 1197.2(2), c = 1278.1(3) pm, α = 69.79(2), β = 72.67(2), γ = 75.79(1)° and Z = 2. The crystal structure has been refined to RF = 0.032 for 3857 reflections.The structure may be described as a layerlike packing of polypseudohalide anions I(ICN)2
- and of complex cations [K(Crypt-2.2.2)]+.
Neue Synthesewege zu neutralen gemischtsubstituierten Eisen-Schwefel-Clustern / Novel Synthetic Pathways to Neutral Mixed-Ligand Iron-Sulfur Clusters
Authors: Harmjanz M. , Junghans C. , Opitz U.-A. , Bahlmann B. , Pohl S.
Published: February 2015

The reaction of [Fe(NiSiMe3)2)2] with thiols RSH, elemental sulfur, and neutral ligands L (with sulfur donor atoms, e. g. thiourea derivatives) gives [Fe4S4(SR)2L2] clusters in high yields. The structure of [Fe4S4(2.4.6-(C3H7)3C6H2-S)2(dpdmi)2] (dpdmi: diisopropyldimethyl- imidazolthion) was determined by X-ray crystallography.

When [Fe4S4I4]2- is reacted with a large excess of PMePh2 or PMe2Ph [F6S6I2(PMePh2)4] and [Fe6S6l2(PMe2Ph)4]. respectively, are obtained in nearly quantitative yield. Basket-like structures of the [Fe6S6]2+ cores were detected by X-ray structure analysis. While [Fe4S4(SR)4]2- clusters do not react with phosphanes at ambient temperature 2:2 functional­ized species like [Fe4S4(SR)2(tmtu)2] lead to basket-type clusters [Fe6S6(SR)2(PR3)4].
Synthese und Kristallstruktur des funktionalisierten Molybdän(VI)- Alkin-Komplexes [MoCl4(Ph – C ≡ C-Se- C4H9)(SEt2)] / Synthesis and Crystal Structure of the Functionalized Molybdenum Alkyne Complex [MoCl4(Ph-C≡C-Se-C4H9)(SEt2)]
Authors: Platea Michael , Dehnicke Kurt , Abram Sonja , Abramb Ulrich
Published: February 2015

[MoCl4(Ph-C≡C-Se-C4H9)(SEt2)] has been prepared by the reaction of trans-[MoCl4(SEt2)2] with Ph-C≡C-Se-C4H9 in dichloromethane solution. The complex was characterized by IR spectroscopy and by a crystal structure determination. Space group P21/c. Z = 4. structure solution with 4595 independent reflections. R = 0.057 for reflections with I > 2σ(I). Lattice dimensions at -65°C: a = 1002.8(2). b = 730.74(5), c = 2703.1(7) pm. β = 95.78(1)°. The complex has a molecular structure in which the molybdenum atom is seven-coordinate by four chlorine ligands, by the two alkyne carbon atoms, and in irons position to the latter by the sulfur atom of the thioether molecule. The MoC bond lengths of 190.2 and 200.9 pm are surprisingly different.
The Structural Side of Conjugation in Some Stable Primary Enamines and Related Systems
Authors: Kowalski Dorothee , Frohlich Roland , Erker Gerhard
Published: February 2015

The structures of 1,6-diamino-1,6-diphenyl-1,3,5-hexatriene (2) and its 1,6-bis(N.N-bistrimethylsilylamino)-derivative (3) are compared. The X-ray crystal structure analyses of 2 and 3 show that turning off the conjugation with the nitrogen lone pairs by orthogonal orientation of the R2N-plane has no measurable effect on the structural features of the framework of the central planar carbon π-system. In a related substituent-stabilized primary enaminc (4) a slightly elongated C=C bond is found by X-ray diffraction.
Synthese, Kristallstruktur und Eigenschaften von 1,1,3,3,3-Pentaamino-1-oxo- 1λ5 ,3λ5-diphosphaz-2-en, (NH2)2(O)P-N=P(NH2)3 / Synthesis, Crystal Structure, and Properties of 1,1,3,3,3-Pentaamino-1-oxo-1λ5, 3λ5-diphosphaz-2-ene, (NH2)2(O)P-N=P(NH2)3
Authors: Stock N. , Schnick W.
Published: February 2015

Coarse crystalline (NH2)2(O)P-N=P(NH2)3 is obtained from a NH3 saturated CH2Cl2 suspension of (NH2)2(O)P-N=P(NH2)3 NH4Cl at room temperature. (NH2)2(O)P-N=P(NH2)3·NH4Cl is synthesized by slow addition of Cl2(O)P-N=PCl3 to a solution of NH3 in CH2Cl2 at -78 °C. Excess NH4Cl is removed by treatment with HNEt2 followed by extraction with CH2Cl2. The crystal structure of (NH2)2(O)P-N=P(NH2)3 has been determined by single crystal X-ray methods (P21/c; a = 1462.8(3), b = 944.8(2), c = 1026.9(2) pm, β = 110.69(3)°; Z = 8). In the unit cell there are two crystallographically unique molecules. They form a three dimensional network by intermolecular hydrogen bonding interactions (N-H···N ≥ 313 pm. N-H···O ≥ 293 pm). The investigation of the thermal properties shows decomposition with evolution of NH3 above 80 °C.
Über einige Aluminiumbromid-Ether-Addukte: Strukturen in Lösung und im festen Zustand / Aluminium Bromide Ether Adducts: Structures in Solution and in the Solid State
Authors: Jakobsmeier Linda , Krossing Ingo , Nöth Heinrich , Schmidt Martin J. H.
Published: February 2015

Monoglyme forms a molecular 1:1 adduct with AlBr3 which dissociates into the ions AlBr2(DME)2
+ and AlBr4
- in DME, CH2Br2 and CDCl3 as solvents. A hexacoordinated Al center is present in the solid adduct AlBr3·diglyme. The oxygen and bromine atoms are arranged in a meriodional configuration as shown by X-ray crystallography. However, in solution dissociation occurs into AlBr2(diglym)2
+ and AlBr4
-. Not unexpectedly, AlBr3 forms the adduct AlBr3·2THF with tetrahydrofuran. The dioxane adduct AlBr3·diox is polymeric in the solid state and has a chain structure with pentacoordinated trigonal-bipyramidal Al centers. The Br atoms are arranged in a slightly distorted trigonal plane. In solution, the presence of tetracoordinated Al is indicated by 27AI NMR spectroscopy. AlBr3 cleaves one of the C-O bonds of 12-crown-4 leading to the dimer of ω-bromo-tetra(ethyleneoxy)aluminium dibromide. This dimer contains pentacoordinated Al centers as proven by X-ray structure analysis. In contrast, the adduct of AlBr3 with 15-crown-5 is most likely an ionic compound, and is best described as [AlBr2(15-crown-5)]AlBr4 based on 27Al NMR and IR data.
Die Kristallstruktur von 2,4-Diaminovinamidinium-bis-tetrachloroferrat(III), (C9H16N4) [FeCl4]2 / The Crystal Structure of 2,4-Diaminovinamidinium Bis-tetrachloroferrate(III), (C9H16N4)[FeCl4]
Authors: Feist Michael , Trojanov Sergej , Kemnitz Erhard
Published: February 2015

(davaH2)[FeCl4]2 crystallizes at room temperature from aqueous solutions of 2,4-diaminovinamidinium hydrochloride, (davaH)Cl, and FeCl3 in 3M HCl in the orthorhombic space group Pca21 with a=14.108(3), b = 16.502(3), c = 18.919(4) Å, Z=8. The structure consists of diprotonated tricyclic (davaH2)2+ cations and slightly distorted tetrahedral [FeCl4]- anions. The cations are bent around the central heptacycle forming boat-like units. One of the two independent cations is disordered between two positions. Some interatomic distances N···Cl are interpreted in terms of N-H···Cl hydrogen bonds.
Ungewöhnliche Koordination am Kalium des 18-Krone-6 Komplexes von Tetraphenyldiselenoimidodiphosphinat und der analogen Schwefelverbindung / Unusual Potassium Coordination in the 18-Crown-6 Tetraphenyldiselenoimidodiphosphinate Complex and its Sulfur Analogue
Authors: Ebert Klaus H. , Cea-Olivares Raymundo , García-Montalvo Verónica , Espinosa-Perez Georgina , Estrada Mirna R. , Novosad Josef , Woollins J. Derek
Published: February 2015

A [K(18-crown-6)] salt of the (Ph2PSe)2NH ligand was obtained by reaction of [K(Ph2PSe)2N] with 18-crown-6 [monoclinic, space group C2/c with the cell parameters a = 20.310(2), b = 8.894(2), c = 22.978(3) Å, β = 114.66(2)°, and Z = 4], The potassium ion has the rare coordination number 10. It is coordinated to the six oxygen atoms of the crown ether and to four carbon atoms, two from each of the two anionic ligands neighboring the cationic moiety.
Dithio- und Thionester, 63 [1] Reduktive Dimerisierung von Aryldithiocarbonsäureestern zu Bis(alkylthio)stilbenen / Dithio- and Thionoesters, 63 [1] Bis(alkylthio)stilbenes by Reductive Dimerisation of Aryldithiocarboxylic Acid Esters
Authors: Hartke Klaus , Bien Notker , Weller Frank
Published: February 2015

Reaction of o- and p-alkyl substituted dithiobenzoic esters 5 with LDA and methyl iodide lead to the formation of the 1,2-bis(methylthio)stilbenes 9/10 and 16 by reductive dimerisation. The p-methyl dithiobenzoic ester 15b, however, suffers a Claisen condensation with lithium hexamethyldisalazane to yield the stilbene derivative 17. Even the o-methyldithiobenzoic acid 19 is reductively dimerized by LDA giving after methylation a mixture of the stilbenes 9a/10a and 20.
Syntheses and Reactions of Heterometallic Complexes of Nickel and Copper with Tetrathiotungstates. The Molecular Structures of [Ph4P]2[S2W(μ-S)2Ni(S2)] and W(μ-S)4Cu2(PPh3)4·py
Authors: Jin Guo Xin , Xin Quan Xin , Wang Bo Yi
Published: February 2015

Reaction of [Ph4P]2WS4 with NiCl2 in methanol solution in the presence of NaOCH3 leads to the formation of [Ph4P]2 [S2W(μ-S)2Ni(S2)] (I). A similar reaction between (NH4)2WS4 and NiCl2 under O2 atmosphere in the presence of Ph4PCl or nBu4NCl affords [Ph4P]2{[(S2)W(O)(μ-S)2]2Ni} (Ila) and [ nBu4N]2{[(S2)W(O)(μ-S)2]2Ni} (lIb). Under argon the same reaction gives [Ph4P]2[Ni(WS4)2] (IlIa) and [nBu4N]2[Ni(WS4)2] (Illb). [Ph4P]2[Ni(WOS3)2] (IV) and [Ph4P]2[Ni(WO2S2)2] (V) can be prepared from the reaction of [Ph4P]2WOS3 and [Ph4P]2WO2S2 with NiCl2. Treatment of (NH4)2WS4 with CuCl in the presence of PPh3 in boiling pyridine produces W(μ-S)4Cu2(PPh3)3 (VI), which can further react with excess PPh3 to give W(μ-S)4Cu2(PPh3)4·py (VII). Complex I crystallizes in the space group P21/n with the cell parameters: a = 20.049(4), b = 17.010(4), c = 14.311(7) Å; β = 110.24(3)° and Z = 4; R = 0.058 for 4267 independent reflections. The structural study confirms that complex I contains two terminal sulfide ligands, two bridging sulfide ligands, a side-on disulfide ligand, and a planar central W(μ-S)2Ni four membered ring. Complex VII crystallizes in the space group C2/c with the cell parameters: a = 26.436(8), b = 20.542(6), c = 19.095(8) Å; β = 128.00(3)° and Z = 4; R = 0.080 for 3802 independent reflections. The structural study reveals a perfect linear arrangement of the three metal atoms Cu-W-Cu.
Notizen: The Auration of Dimethylsulfide
Authors: Sladek Alexander , Schmidbaur Hubert
Published: February 2015

Dimethylsulfide reacts with (triphenylphosphine) gold(I) trifluoromethanesulfonate to give quantitative yields of the mixed ligand complex [(Ph3P)Au(SMe2)]+O3SCF3
- (1). The structure of compound 1 has been determined by an X-ray crystal structure analysis. The lattice contains independent anions and (monomeric) cations, which have a linear P-Au-S axis. Attempts to produce a binuclear. dicationic complex through addition of a second equivalent of [(Ph3P)Au]+ failed and lead to decomposition products including [(Ph3P)2Au]+O3SCF3
-.
Notizen:Neue Verbindungen mit CeNiSi2-Struktur / New Compounds with C eNiSi2-Type Structure
Authors: Johrendt Dirk , Lux Christine , Mewis Albrecht
Published: February 2015

The compounds BaPdAs2 (a = 4.678(1), b = 17.330(2), c = 4.574(1) Å), BaPdSb2 (a = 4.877(1), b = 18.583(2), c = 4.889(1) Å) and BaPtAs2 (a = 4.660(1), b = 17.119(2), c = 4.608(1) Å) were prepared by heating mixtures of the elements and investigated by X-ray methods. They are isotypic and crystallize in the CeNiSi2-type structure (Cmcm), also called the BaCuSn2-type.
Amphiphilic Carbohydrate-Based Mesogens, 12 [1] High-Yield Synthesis of Mesogenic 1-O-Alkanoyl-D/L-Xylitols
Authors: Dahlhoff Wilhelm V. , Radkowski Karin , Dierking Ingo , Zugenmaier Peter
Published: February 2015

The equilibrium mixture of 1,2:3,4- and 1,3:2,4-di-O-ethylboranediyl-D/L-xylitols 1 and 1′ obtained on reaction of three equivalents of xylitol with two equivalents of triethylboroxin, reacts with alkanoyl chlorides (heptanoyl-dodecanoyl) to give equilibrium mixtures of the O-ethylboranediyl protected l-O-alkanoyl-D.L-xylitols 2,2′ after vacuum distillation. Deprotection of the latter affords the title amphiphilic esters 3 which melt to give the smectic A liquid-crystalline phase.
Methanolothermale Synthese von Cs4As2Te6, des ersten Alkalimetall- Telluridoarsenats mit As-As- und Te-Te-Bindungen / Methanolothermal Synthesis of Cs4As*Te6, the First Alkali Metal Telluridoarsenate with As-As and Te-Te Bonds
Authors: Wachhold M. , Sheldrick W. S.
Published: February 2015

Reaction of Cs2CO3 and As2Te3 in methanol at 145°C affords the telluridoarsenate(II) Cs4As2Te6. A trans conformation is observed for the centrosymmetric As2Te4−
6 anions, which consist of two ѱ-tetrahedralo As(As)(Te2)Te units with a common As-As bond. The terminal As-Te distance of 2.554(2) Å is much shorter than the As-Te distance of 2.691(2) Å to the Te2 unit, which exhibits a Te-Te bond length of 2.744(2) Å. Both of the independent cations are coordinated in an irregular manner by eight Te atoms.
Tetraphenylphosphonium-ikosioctabromooctaantimonat(III), (PPh4)4Sb8Br28 / Tetraphenylphosphonium Ikosioctabromooctaantimonate(III), (PPh4)4Sb8Br28
Authors: Fachbereich Biologie-Chemie, Universität Gh, D- Kassel Wolfgang , Fachbereich Biologie-Chemie, Universität Gh, D- Kassel Ulrich
Published: February 2015

The title compound was obtained by the reaction of PPh4Br, Sb2Se3, and bromine in dichloromethane. Its crystal structure was determined by X-ray diffraction. Crystal data: a = 1249.1(2), b = 1307.8(2), c = 2152.3(4) pm, α = 102.93(2), β = 100.83(2), γ = 100.42(2)°, Z = 2, triclinic, space group P1̄. (PPh4)4Sb8Br28 is isotypic with (PPh4)4Sb8I28. The Sb8Br28
4- ion can be taken as the association product of eight SbBr3 molecules with four Br− ions. Each Sb atom has a distorted octahedral coordination with three shorter (252 to 274 pm) and three longer (300 to 353 pm) Sb-Br bonds. The octahedra share common edges in two parallel rows of four octahedra each. The arrangement of the 28 bromine atoms corresponds to a section of a closest packing of spheres.
Stereoselektive Pudovik-Reaktion von 5,6-Benzo-2//-l-methyl-3- (2’-chlorethyl)-2-oxo-1,3,2λ4-diazaphosphorin-4-on mit einem 3-Thiazolin und MPL-chromatographische Isolierung des Überschußdiastereomers / Stereoselective Pudovik Reaction of 5,6-Benzo-2H-1-methyl-3-(2’-chloroethyl)-2-oxo-1,3,2λ4-diazaphosphorin-4-one with a 3-Thiazoline and MPL-Chromatographical Isolation of the Major Diastereomer
Authors: Gröger Harald , Wilken Jörg , Martens Jürgen
Published: February 2015

The modified Pudovik reaction of 5,6-benzo-2H-1-methyl-3-(2′-chloroethyl)-2-oxo-1,3,2λ4-diazaphosphorin-4-one with a 3-thiazoline furnishing the corresponding 5,6-benzo-2H-1-methyl- 3-(2′-chloroethyl)-2-oxo-2-(3-thiazolidin-4-yl)-1,3,2λ4-diazaphosphorin-4-one 4 and the medium pressure liquid column chromatographical (MPLC) isolation of the major diastereomer is described. The relative stereochemistry at the centres PI and Cl was determined by X-ray structure determ ination of three racemic modifications (a total of seven independent molecules).
Thermolyse und Photolyse von cyclischen Diazoverbindungen [1] / Thermolysis and Photolysis of Cyclic Diazo Compounds [1]
Authors: Stachel Hans-Dietrich , Poschenrieder Hermann , Redlin Jutta
Published: February 2015

The rhodium-catalyzed decomposition of the diazoketones 4 in tert-butyl alcohol at 130 °C furnishes the m onoenolethers 5 and, after deprotection, the aci-reductones 6. In absence of intercepting agents the intermediate carbenes preferentially undergo Wolff rearrangement with ring contraction. In this case the β-thiolactone 10b or the β-lactone 13 or the β-lactam 14 are thermolysis products of the corresponding diazoketones. During photolysis of the diazoketones 4d/4g in presence of alcohols the 2-azetidinones 10c/d are formed.
Die Kristallstruktur des Phosphaniminato-Komplexes [TiCl3(NPPh3)•TiCl4]2 / Crystal Structure of the Phosphorane Iminato Complex [TiCl3(NPPh3)•TiCl4]2
Authors: Weller Frank , Schmock Fritjof , Dehnicke Kurt
Published: February 2015

The title compound was prepared from Me3SiNPPh3 and an excess of titanium tetrachloride. It forms yellow-orange crystals, which were characterized by IR spectroscopy and by crystal structure determination. Space group P21/n, Z = 2; lattice dimensions at 20°C: a = 1189.2(1), b - 1718.5(1), c = 1238.1(1) pm, β = 93.363(7)°. The compound forms centrosymmetric dimers in which the titanium atoms are triply and doubly bridged by chlorine atoms to give face- and edgesharing octahedra, respectively. In the linear units [Ti]=N =PPh3 the Ti-N bond distance of 171.6(3) pm corresponds to a double bond.
Structure Refinement of Rubidium Periodate at 297 and 150 K
Authors: Waal Danita de , Range Klaus-Jürgen
Published: February 2015

The scheelite-type structure of rubidium periodate, RbIO4, has been confirmed and refined from single-crystal X-ray data at two temperatures. The compound crystallizes tetragonally, space group I41/a, with a = 5.897(1), c = 12.876(3) Å at 150 K and a = 5.910(1), c = 13.021(3) Å at 297 K, respectively. Only small changes are observed for the structural parameters at low temperatures, but a significant decrease could be observed in the anisotropic displacement factors.
Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalysen von trans-[PtX2(acac)2], X = CI, Br, I, SCN / Crystal Structures, Vibrational Spectra and Normal Coordinate Analyses of trans-[PtX2(acac)2], X = Cl, Br, I, SCN
Authors: Rickert D. , Preetz W.
Published: February 2015

The crystal structures of trans-[PtCl2(acac)2](monoclinic, space group P21/c, a - 7.616(5), b = 12.759(5), c = 7.892(5) Å, β = 118.459(5)°, Z = 2), trans-[PtBr2(acac)2] (triclinic, space group P1̅, a = 7.502(5), b = 7.665(5), c = 8.155(5) Å, α = 114~508(5), β = 94.537(5), γ = 117.669(5)°. Z = 1) and trans-[Pt(SCN)2(acac)2] (triclinic, space group P1̅ , a = 7.9095(10), b = 7.9393( 10), c = 7.9631 Å, a = 114.051 (10), β = 100.955(10), γ = 100.573(10)°, Z = 1) have been determined by single crystal X-ray diffraction analysis. The crystal structure of trans- [Ptl2(acac)2] is known from the literature. To enhance the spectroscopic resolution, the IR and Raman spectra of the four complexes have been measured at low temperature (10 K). Using the X-ray data, normal coordinate analyses based on a modified valence force field have been performed and the normal modes of vibration for the octahedral skeleton [PtX2O4] have been assigned. With a set of 19 or 23 force constants taking into account the inner-ligand vibrations a good agreement between observed and calculated frequencies has been achieved. The valence force constants are e.g.fd (PtCl) = 2.16, fd (PtBr) = 1.45, fd (PtI) = 1.01, fd (PtS) = 1.80 mdyn/Å, and fd (PtO) ranges from 1.89 to 1.91 mdyn/Å.
Zur Kenntnis eines Barium-Oxoniobat-Tellurats: Ba2Nb2TeO10 / On a Barium-Oxoniobate-Tellurate: Ba2Nb2TeO10
Authors: Wedel B. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of Ba2Nb2TeO10) have been prepared by solid state reactions in air. X-ray investigations led to orthorhombic symmetry, space group D15
2h-Pbca, a = 7.242(4), b = 12.433(3), c = 9.932(3) Å. Z = 4. Nb5+ and Te6+ show octahedral coordination by O2- . The crystal structure is characterized by planes of edge- and corner-sharing NbO6- and TeO6octahedra. It is shown that in spite of nearly identical lattice constants of Ba2Nb2TeO10 with compounds of the composition M0,5BaNbTe2O9 the so far unknown crystals of these substances may not be derived from the Ba2Nb2TeO10 type.
Zur Kristallchemie der Barium-Oxometallat-Tellurite: Ba2M6Te2O21 (M = Niob und Tantal) / On the Crystal Chemistry of the Barium Oxometallate-Tellurites Ba2M6Te2O21 (M = Niobium and Tantalum)
Authors: Wedel B. , Miiller-Buschbaum Hk.
Published: February 2015

Single crystals of Ba2Nb6Te2O21 (I) and Ba2Ta6Te2O21 (II) have been prepared by solid state reactions in air. X-ray investigations led to monoclinic symmetry, space group C3
2h -C2/m, (I): a = 16.699(3), b = 5.671(2), c = 9.611(2) Å, β = 96.92(2), (II): a = 16.655(8), b = 5.667(2), c = 9.576(4) Å, β = 96.64(7), Z = 2. Nb5+ or Ta5+ show octahedral and Te4+ a one sided triangular coordination by O2- . The position and distance of the lone pair on Te4+ have been estimated by calculations of the Coulomb terms of the lattice energy. The polyhedron around Ba2+ may be described by a triply capped BaO8 cube. The crystal structures are dominated by a 3
∞ [Nb6O21]12- network with incorporated Ba2+ and Te4+ ions.
Neue Einsichten zur Stabilisierung des Hulsit-Strukturtyps am Beispiel von MnII,2MnIII(BO3)O2 und MnIISrMnIII(BO3)O3 / New Insights into the Stabilization of the Hulsite Structure During Crystal Structure Determination of MnII
2MnIII(BO3)O2 and MnIISrMnIII(BO3)O2
Authors: Utzolino Anne , Bluhm Karsten
Published: February 2015

The compounds MnII
2MnIII(BO3)O2 (I) and MnIISrMnIII(BO3)O2 (II) were prepared by using a B2O3 flux technique. Single crystals were investigated by X-ray diffraction. I showed orthorhombic symmetry, space group D9
2h - Pbam (No. 55), a = 926.0; b = 1241.5; c = 304.96pm ; Z = 4 and II monoclinic symmetry, space group C1
2h - P2/m (No. 10), a = 1107.5; b = 311.04; c = 542.93 pm, β = 95,10(2)°; Z = 2. MnII
2MnIII(BO3)O2 i is isotypic with the mineral Ludwigite while MnnIISrMnmIII(BO3)O2 is isostructural with the mineral Hulsite. In the structure of MnII2Mnlll(BO3)O2 (I) all metal point positions showed octahedral oxygen coordination, one point position is occupied by Mn3+ . The structure of Mnll
2Sr2Mnlll
2(BO3)2O4 (II) contains five octahedrally coordinated metal sites, three of them statistically occupied by Mn2+ or Mn 3+ and Sr2+. The incorperation of Sr2+ seems to be responsible for the Hulsite structure. Both structures contain isolated, trigonal planar BO3 units and oxygen atoms that are not coordinated to boron.
Metallkomplexe mit Guanidinderivaten als Liganden: Kristallstrukturen von [Zn(cnge)2(SCN)2] · 2H2O und Zn(eoge)Br2 (enge = Cyanoguanidin; eoge = 1-Ethoxyiminomethylguanidin) / Metal Complexes with Guanidine Derivatives as Ligands: Crystal Structures of [Zn(cnge)2(SCN)2]·2H2O und Zn(eoge)Br2 (cnge = Cyanoguanidine; eoge = 1-Ethoxyim inom ethylguanidine)
Authors: Pickardt Joachim , Kühn Britta
Published: February 2015

Crystals of |Zn(cnge)2(SCN)2]-2H2O (1) were obtained by evaporation of an aqueous solution of Z n(SO4)·7H2O , KSCN, and cyanoguanidine. Crystals of Zn(eoge)Br2 (2) were obtained by reaction of ZnBr2 and cyanoguanidine in ethanol/water. Both compounds are monoclinic, space group C2/c, 1: Z = 4, a = 1919.6(7), b = 467.3(2), c = 1838.5(6) pm, β = 112.99(3)°, 2: Z = 8, a = 1799.5(6), b = 878.7(2), c = 1367.2(5) pm, β = 101.52(3)°. In 1 each Zn is bonded to two cyanoguanidine molecules and via the N atoms to two NCS groups. Intermolecular hydrogen bonds lead to chains along the a-axis, and these chains are again connected via hydrogen bonds to the two crystal water molecules. In the course of the formation of 2, the cyanoguanidine reacted with the ethanol to form 1-ethoxyiminomethylguanidine. This ligand forms chelate rings with the Zn atoms, which are tetrahedrally coordinated by the two imino N atoms of the ligand and by two bromine atoms.
Photochemische Reaktionen von Übergangsmetall-Organyl-Komplexen mit Olefinen, XVI [1]: Photochemisch induzierte Cycloadditionen von Diphenylacetylen an Tricarbonyl(η5-2,4-dimethyl-2,4-pentadien-1-yl)mangan / Photochemical Reactions of Transition Metal Organyl Complexes with Olefins, XVI [1]: Photochemically Induced Cycloadditions of Diphenylacetylene to Tricarbonyl(η5-2,4-dimethyl-2,4-pentadien-1-yl)manganese
Authors: Kreiter Cornelius G. , Koch Ernst-Christian , Frank Walter , Reiß Guido J.
Published: February 2015

Upon UV irradiation in THF at 208 K tricarbonyl(η5-2,4-dimethyl-2,4-pentadien-1-yl)- manganese (1) yields solvent stabilized, very reactive dicarbonyl(η5-2,4-dimethyl-2,4-pentadien-1-yl)(tetrahydrofuran)manganese (2), which reacts in situ with one or two molecules of diphenylacetylene (3) and yields four manganese complexes and 1,3-dimethyl-5,6-diphenyl-bicyclo[3.2.1]oct-2-ene-7-one (5), which were separated by HPL chromatography. In addition to tricarbonyl η5-4,6 -dimethyl-1,2-diphenyl-cyclohepta-2,4-dien-1-yl)manganese (4) formed by [5+2]cycloaddition and successive 1,4-H shift, tricarbonyl{ 1′,2′,5′-η-5-methyl-2,3 -diphenyl-5- (2′-methyl-4′,5′-diphenyl-penta-1′,4′-dien-1′,5′-diyl)cyclopent-2-en-1 -one-κ-O}manganese (6) is isolated with a ligand, formed from 2,4-dimethyl-2,4-pentadien-1-yl, two units of 3 and one carbon monoxide. The ligands of tricarbonyl{ 1-4,2′-η-4,6 -dimethyl-1,2-diphenyl-5-(E-1′,2′- diphenyl-vinylen)cyclohepta-1,3-diene}manganese (7), and tricarbonyl{η5-4,6 -dimethyl-1,2-diphenyl-7-(E-1′,2′-diphenyl-vinyl)cyclohepta-2,4-dien-1-yl}m anganese (8) are formed from 2,4-dimethyl-2,4-pentadien-1-yl and of two molecules of 3 each. The crystal and molecular structures of 5 and 6 have been determined by single crystal X-ray diffraction. 5 crystallizes in the triclinic space group P1̅ , a = 992.0(2) pm, b = 996.8(2) pm, c = 1021.0(2) pm, a = 77.67(3)°, β = 61.17(3)°, γ = 88.68(3)°. Complex 6 crystallizes also in the triclinic space group P1̅ ,a = 1023.2(2) pm, b - 1113.8(2) pm, c = 1567.9(3) pm, α = 82.88(3)°, β = 86.93(3)°, 7 = 63.53(3)°. The constitutions of 4, 7 and 8 were elucidated from the IR, NMR and mass spectra. Possible formation mechanisms for the compounds 4-8 are proposed. Complex 7 shows hindered rotations of two phenyl groups with different barriers of energy ΔG≠
316 = 68.8 kJ/mol, „ΔH≠ = 67.9 ± 0.7 kJ/mol, ΔS≠ = -2 ± 2 J/mol · K and ΔG≠
296 = 60.6 kJ/mol, ΔH≠ = 57.7 ± 1.0 kJ/mol, ΔS≠ = -10 ± 2 J/mol·K due to steric interactions.
Wechselwirkungen in Kristallen, 88 [1 - 3] Donator/Akzeptor - Komplexe von Alkylbenzolen, Pyren oder Perylen mit Tetrahalogen-p-benzochinonen: Strukturen und Eigenschaften / Interactions in Crystals, 88 [1 -3] Donor/Acceptor Complexes of Alkylbenzenes, Pyrene or Perylene and Tetrahalogen-p-benzoquinones: Structures and Properties
Authors: Bock Hans , Sievert Mark , Schödel Holger , Kleine Markus
Published: February 2015

The following mixed-stack donor/acceptor complexes {D · · · A }∞ have been crystallized and their structures determined: { 1 ,2,4,5-tetramethylbenzene · · · tetrabromo-p -benzoquinone}∞ , {hexamethylbenzene · · · tetrabromo-p-benzoquinone}∞ , { ( 1 ,2 ,4,5-tetramethyl-benzene)2 · · · tetrachloro -p -benzoquinone}∞ , {pyrene · · · tetrafluoro-p-benzoquinone}∞ , {pyrene · · · tetrabromo-p-benzoquinone}∞ and {perylene · · · tetrabromo-p-benzoquinone}∞ . They exhibit an interesting lattice packing, especially the 2:1 tripeldecker sandwich of tetrachloro-p-benzoquinone, which crystallizes in a herringbone pattern. Their interplanar distances are around 340 pm, i. e. two van der Waals π radii. None of them , however, exhibits in neither the donor nor the acceptor components significant structural changes due to complex formation. Their colours range from orange-red to black in the crystal and to green in H2CCl2 solution. Their long-wavelengths charge transfer absorption maxim a correspond to a lowering in excitation energy of up to 2 eV relative to that of the components. The different charge transfer in the ground and excited states of the donor/acceptor complexes investigated is further discussed referring to data such as cyclovoltammetric reduction potentials as w ell as to results from semiempirical calculations based on the crystal structure data determined and including configuration interaction.
Die Kristallstruktur von CsNaTe / The Crystal Structure o f CsNaTe
Authors: Fischer Karsten , Feldbaum -Möller Elisabeth , Vogt Petra , Wachhold Michael , Winter Volker , Sabrowsky Horst
Published: February 2015

The crystal structure of CsNaTe has been determined by X-ray diffraction of single crystals. The hygroscopic CsNaTe crystallizes in the tetragonal space group P4/nmm (Z = 2) with the cell parameters a = 527.6(1) and c = 847.8(2) pm. The structure was determined from 237 independent reflections by Patterson and Fourier methods (R1 = 0.065; wR2 = 0.080).
Die Kristallstruktur von [Na4(OSiPh3)4(H2O)3] / The Crystal Structure of [Na4(OSiPh3)4(H2O)3]
Authors: Mommertza A. , Dehnickea K. , Magull J.
Published: February 2015

Colourless single crystals of the title compound are obtained from a saturated solution of NaOSiPh3 in toluene in a humid atmosphere. We have characterized [Na4(OSiPh3)H2O)3] by IR spectroscopy and by a crystal structure determination. Space group R3, Z = 6 , R = 0.056. Lattice dimensions at -70°C: a = b = 1540.3 pm, c = 2639.6 pm. The compound has the structure of a Na4O4 heterocubane which is only slighty distorted and in which one of the sodium atoms is not hydrated and shows coordination number three.
Über ein Blei-Kupfer-Tellurat PbCu3TeO7 mit Cu2+ in deformiert tetragonal pyramidaler und tetraedrischer Sauerstoffkoordination / On a Lead Copper Tellurate PbCu3TeO7 Containing Cu2+ in Distorted Square Pyramidal and Tetrahedral Oxygen Coordination
Authors: Wedel B. , Müller-Buschbaum Hk.
Published: February 2015

PbCu3TeO7 has been prepared from the element oxides by solid state reaction in air. Single crystal X-ray work led too orthorhombic symmetry, space group D2h
16-Pnma, a = 10.488(1), b = 6.353(2), c = 8.813(2) Å, Z = 4. Cu(1)O5 square pyramids and TeO6 octahedra are members of the anionic part of the crystal structure, Cu(2) atoms show tetrahedral coordination by oxygen. The Cu(2)2+ and the Pb2+ cations are incorporated into a [Cu(1)2TeO7] network. PbCu,TeO7 can thus be viewed as a lead copper oxocuprate(II) tellurate. Calculations of the Coulomb terms of lattice energy reveal two possible positions for the lone pair of electrons at Pb2+.
Darstellung und Charakterisierung von 2-substituierten 5,6-Benzo-1-methyl- 3-R-1,3,2-diazaphosphorin-4-onen (R = 2-Morpholinoethyl, 1-Adamantyl) mit Phosphor in den Koordinationszahlen drei, vier und fünf / Synthesis and Characterization of 2-Substituted 5 ,6-Benzo-1-methyl-3-R -1,3,2- diazaphosphorin-4-ones (R = 2-Morpholinoethyl, 1-Adamantyl) Containing Phosphorus with Coordination Numbers Three, Four and Five
Authors: Borkenhagen Frank , Neda Ion , Thönnessen Holger , Jones Peter G. , Schmutzler Reinhard
Published: February 2015

The reaction of N-methylisatoic anhydride with 2-morpholinoethylamine or 1-aminoadamantane furnished N-methyl-N′-(2-morpholinoethyl)anthranilamide 1 and N-methyl-N′- ( l-adamantyl)anthranilamide 2, respectively. 1 and 2 are intermediates in the synthesis of the 2-chloro-3-methyl-1,3,2 λ3-diazaphosphorinones 3 and 4 by reaction of 1 and 2 with PCI3. The reaction of 3 with bis(2-chloroethyl)amine hydrochloride/triethylamine or (2-chloroethyl)amine hydrochloride/triethylamine formed the 2-substituted diazaphosphorinones 5 and 6. Hydrolysis of 3 led to the 2-oxo-λ4P-compound 7. The reaction of 6 with hexafluoroacetone furnished the (λ5) phosphorane 8. 5 reacted with C7H8Cr(CO)4 to form complex 9 whereas oxidation of 5 with the H2O2: urea 1:1 adduct yielded the phosphoryl compound 10. The crystal structure of 1 displays two independent molecules that show different chain conformations. Both molecules form chains parallel to the y-axis by intermolecular N (amide)-H···O(amide) bonds. The crystal structure of 6 shows a half-boat conformation for the phosphorinone ring; the P atom lies out of the plane. Again the molecules are linked by H-bonds into chains parallel to the y-axis.
Metallkomplexe von Farbstoffen, VII [1] Triphenylphosphan-Gold(I)-Komplexe mit dem Mono- und Dianion von Indigoderivaten / Metal Complexes of Dyes, VII [1] Triphenylphosphine Gold(I) Complexes with the Mono and Dianion of Indigo Derivatives
Authors: Lenz Andreas , Slinkel Karlheinz , Beck Wolfgang
Published: February 2015

Triphenylphosphine gold(I) complexes (Ph3P)Au(4,4′-dichloroindigo-H+) and [(Ph3P)Au]2- (4,4′-dichloroindigo-2H+) and (Ph3P)Au-L (LH = isatin, 5-bromoisatin, 2-indolinone) were prepared and characterized. The structure of the gold(I) complex of the monoanion of 4,4′- dichloroindigo (1) which was determined by X-ray diffraction, shows a slight deviation from the linear P-Au-N [ 169,5(4)°] arrangement with a short Au-N [206(1) pm] and a long Au-O(C) [267(2) pm] distance. In the crystal the complexes 1 and [(nBu3P)(Cl)Pd][indigo-H+) form centrosymmetric pairs with parallel arrangement of the two indigo ligands.
Diyne Cyclization in Camphor Derivatives - Experimental and Theoretical Investigation
Authors: Wagner Gabriele , Heiß Christian , Verfiirth Uwe , Herrmann Rudolf
Published: February 2015

Derivatives of 3-oxo-camphorsulfonimide (1) with two phenylethynyl groups in the endo positions at the carbons C-2 and C-3 were prepared, and their reactivity towards halogenes and titanium chloride was studied. In every case, the two ethynyl groups led to the annulation of a five-membered ring to the bicyclo[2 .2 .1] system in an orientation which depends on the bulkiness of the additional substituent in position 3. NMR studies show that cationic species like 6 and 8 are the first detectable intermediates. They not only contain the fused five-membered ring but also a bond between its exocyclic methylene carbon and an oxygen atom of the sulfonyl group, thus transferring the positive charge mainly to sulfur. Semiempirical calculations (PM3) suggest two intermediates in the formation of such cations.
Asymmetrie Ethynes. Syntheses of Ethynylferrocene Paradigms
Authors: Polin Johann , Schottenberger Herwig , Schwarzhans Karl Eberhard
Published: February 2015

Synthetic methods to bifunctional ethynes have been examined. Direct ethynylation, the Stephens-Castro reaction, the Pd-catalysed Hagihara coupling, transmetalation reactions and nucleophilic additions have been evaluated in the preparation of substituted ferrocenylethynes with intended use of these materials in electrochemical and nonlinear optical investigations. Asymmetric ferrocenylethynes are promising candidates for applications in contemporary materials science. Synthetically, 1,4-bis(ferrocenylethynylene)benzene (1), 1,3,5-tris(ferrocenylethynylene) benzene (2), and 9 ,10-bis(ferrocenylethynylene)anthracene (3) are obtained in high yields, whereas 4-ferrocenylethynylene-2,3,5,6-tetrafluorostyrene (4) and potassium (ferrocenylethynylene) triphenyl borate (5) are accessible in only moderate yields. Further extension of this chemistry to additional heteronuclear bimetallic coordination compounds has been attempted, but without success due to severe difficulties in both preparation and characterization of these materials.
Heterometallische Mehrkernkomplexe von Zink und Cadmium mit cis-[Cr(OH)2(en)2]+-Liganden / Heterom etallic Polynuclear Complexes of Zinc and Cadmium with cis-[Cr(OH)2(en)2]+ Ligands
Authors: Rominger Frank , Thewalt Ulf
Published: February 2015

A series of polynuclear heterometallic complexes containing chromium and zinc or cadmium were prepared by the reaction of cis-[CrCl2(en)2]Cl and a zinc or cadmium salt in water and the molecular and crystal structures of 1 to 5 determined by X-ray structure analyses. The products contain chelating or bridging cis-[Cr(OH)2(en)2]+ groups. For the zinc complexes a tetrahedral coordination is observed, and the [Cr(OH)2(en)2]+ units are found to act as bridges. [[ZnCl2(μ-OH)Cr(en)2(μ-OH)]ClO4]n (1) has a chain polymeric structure. [{ZnCl2(μ-OH)Cr(en)2(μ-OH)}2]Cl2 (2) has a cyclic structure. In the case of the cadmium complexes the [Cr(OH)2(en)2]+ units act as chelating ligands. For the three cadmium complexes [Cd3(μ-Cl)4Cl4{Cr(μ3-OH)(μ-OH)(en)2}2]·4H20 (3), [[Cd(μ-Cl)(H2O)2{Cr(μ-OH)2(en)2}](ClO4)(NO3)·2H2O]n; (4), and [Cd2(μ-Cl)2Cl3(H2O)3{ Cr(μ-OH)2(en)2}]n; (5) an octahedral coordination sphere is observed. The cadmium atoms in 3 to 5 are connected by at least one chloro bridge. In the centrosymmetrical pentanuclear complex 3 bridging occurs by face-sharing, and in the chain polymeric complexes 4 and 5 by edge-sharing of the coordination octahedra. In the crystal structures of all complexes a network of hydrogen bonds is observed, which contributes substantially to the stability of the conformation of the chain structures.
Ein neuer Heterocyclus, 2λ3,4λ5-[1,2,4]-Oxadiphosphinin (2), als Ligand eines zweikernigen Eisenkomplexes / A New Heterocycle, 2λ3, 4λ5 -[1,2,4]-Oxadiphosphinine (2), as Ligand of a Binuclear Iron Complex
Authors: Rosche Fred , Heckmann Gernot , Weller Frank , Fluck Ekkehard
Published: February 2015

Preparation and properties of a coordination compound are described, in which a carbonyl group in bis[(dicarbonyl)(μ5-cyclopentadienyl)iron] is substituted by hitherto unknown octa- N-methyl-2λ3,4λ5-[1,2,4]-oxadiphosphinine-2,4,4,6-tetramine (2). The 1H , 31P, and 13C NMR spectra are recorded and discussed in detail. The molecular structure of the iron complex 4 is described and interpreted.
Phosphonio-substituierte Tetrahydro-1,3-diphosphinine und Tetrahydro-1,2,6-azadiphospliinine / Phosphonio-Substituted Tetrahydro-1,3-diphosphinines and Tetrahydro-1,2,6-azaphosphinines
Authors: Jochem Georg , Schmidt Martin , Nöth Heinrich , Schmidpeter Alfred
Published: February 2015

The bis(triphenylphosphonio)propenide cation 1 provides two reactive CH sites in 1,3- position and can be condensed with the bis(dichlorophosphanyl)methylene triphenylphosphorane 2 or the bis(dichlorophosphanyl)aniline 3 to form cationic six-membered rings: A tetrahydro-1,3-diphosphinine (4) with three phosphonio or phosphoranediyl substituents in 2,4,6-position and a tetrahydro-1,2,6-azadiphosphinine (5) carrying two such substituents in 3,5-position. The bromide of the latter was used for an X-ray structure analysis.

The PIII ring members of the cations 4 and 5 can be oxidized in two steps by elemental sulfur to give the monothioxo and dithioxo derivatives 6. 7 and 8, 9. respectively. A crystal of the mixed chloride/bromide of 8 was used for another X-ray structure analysis.
Synthetic Epimers of Ajmaline and Isoajmaline
Authors: Khan M. Ataullah , Raees Humaira
Published: February 2015

Two new epimers of ajmaline (1) and isoajmaline (2) were synthesized by means of tosylation followed by hydrolysis with NaOH/CH3OH. Displacement of tosyl with hydroxyl group yielded C21 epimers of these alkaloids. The structures were identified by various spectroscopic techniques.
Experimental and Computational Studies on Aminoguanidine Free Base, Monocation and Dication, Part I: The Crystal and Molecular Structure of Aminoguanidine Monohydrochloride and the ab Initio Structure of the Endiamine Tautomer of Aminoguanidine Free Base
Authors: Koskinen Jere T. , Koskinen Mikko , Mutikainen Ilpo , Mannfors Berit , Elo Hannu
Published: February 2015

The crystal and molecular structure of aminoguanidine monohydrochloride, CN4H7
+.CL- in which aminonoguanidine exists in the monocation form, was determined by single-crystal X-ray diffraction. The structure of the monocation is largely similar to that of aminoguanidine dication as present in previously studied divalent salts. The monocation was found to exist in the form of the tautom er that allows strong resonance in the guanyl group. As compared to the dication, the terminal hydrazine nitrogen atom bears one hydrogen atom less. The monocation is planar, the only atoms deviating from the plane being the hydrogens attached to the terminal hydrazine nitrogen. Quantum chemical calculations on the endiamine tautomer of aminoguanidine free base as well as on aminoguanidine monocation and dication were also perform ed by using the HF and MP2 ab initio methods and also the B3- LYP and B-LYP methods based on density functional theory. On the basis of the calculations, a predicted structure of the endiamine tautom er of aminoguanidine free base is presented
Über CuDy2[B8O16] und CuHo2[B8O16]: Zwei neue „Metaborate“ mit einem ∞
1[B8O16]8--Anion / On CuDy2[B8O16] and CuHo2[B8O16] Two New „Metaborates“ with a ∞
1[B8O16]8-Anion
Authors: Wiesch André , Timm Hauke , Bluhm Karsten
Published: February 2015

Nearly colourless single crystals of the compounds CuDy2[B8O16] (I) and CuHo2[B8O16] (II) have been obtained by a B2O3 flux technique. They crystallize in the structure of CuTb2[B8O16] (I) or in an orthorhombic variant (II). X-ray investigations on single crystals led to the space group C2h
5 - P21/c (Nr. 14) with lattice parameters a = 1025,5(10); b = 836,99(10); c = 621,2(8) pm, β = 90.47(10)°; Z = 2 (I) and D2h
9 - Pbam (Nr. 55) with a = 840,7(2), b = 616,6(2), c = 1022,0(2) pm, Z = 2 (II). The structures contain 1
∞[B8O16]8- chains isolated from each other, which include tri- and tetracoordinated boron. The chains consist of alternating twelve and eight-membered rings of boron and oxygen atoms connected by BO4 units. Dy3+ and Ho3+ are octacoordinated and Cu2+ is hexacoordinated in elongated octahedra by oxygen. The relation between these two structures is discussed.
Zur Kristallchemie der Kupfer(II)-ZinkteIlurate Cu5Zn4Te3O18 und Cu1,5Zn1,5TeO6, mit einer Notiz über Cu1,5Co1,5TeO6 / On the Crystal Chemistry of the Copper(II) Zinc Tellurates Cu5Zn4Te3O18 and Cu1,5Zn1,5TeO6 with a Note on Cu1,5Co1,5TeO6
Authors: Wulff L. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of Cu5Zn4Te3O18 (I), Cu1.5Zn1.5TeO6 (II) and Cu1.5Co1.5TeO6 (III) have been prepared and investigated by X-ray work. The structure of (I) was solved in the monoclinic space group C3
2-C2, a = 14.834(2), b = 8.801(1), c = 10.375(2) Å, β = 93.27(2)°, Z = 4. (II) and (III) crystallize with cubic symmetry, space group Th
7-Ia3̄, a(II) = 9.557(1), a(III) = 9.570(1) Å, Z = 8. (I) shows a complicated structure formed by TeO6 octahedra isolated from each other, Zn2O6 double tetrahedra and Zn2O8 double square pyramids. These polyhedra are incorporated into a network of edge and corner connected stretched CuO6 octahedra. (II) and (III) are isotypic to Cu3TeO6 and have a (Cu/M)3O6 octahedra network, statistically occupied by Cu2+ and Zn2+ or Cu2+ and Co2+.
Synthesis and Crystal Structure of a Novel Neutral Polymeric Lead(II)-thiosemicarbazonato Complex
Authors: Castiñeiras Alfonso , Domínguez Ricardo , Bresolin Leandro , Bortoluzzi Adaílton Joao , Burrow Robert Alan , Hörner Manfredo
Published: February 2015

The reaction between lead(II) acetate and 2-acetylpyridine 4N-methylthiosemicarbazone (H4ML) produced a complex of the formula [Pb(4ML)(OOCMe)] with an unusual polymeric structure in which the lead atom is hepta-coordinate, the deprotonated thiosemicarbazone is a tetradentate bridge, and the acetate group both chelates and bridges. The complex crystallizes in the triclinic space group P1̄ with a = 8.860(2), b = 9.394(2), c = 9.783(3) A, α = 108.93(4), β = 98.67(3), γ = 107.87(5)°, V = 704.1(3) Å3 , Z = 2.
Synthese und Charakterisierung des Fulleren-Kokristallisats C60*SiH(C6H5)3/Synthesis and Characterisation of the Fullerene Co-Crystal C60*SiH(C6H5)3
Authors: Waidmann G. , Jansen M.
Published: February 2015

A new fullerene co-crystal C60*SiH(C6H5)3 has been synthesized by crystallisation from a melt of SiH(C6H5)3 and C60 in sealed duran tubes at 80°C. X-ray investigations led to triclinic symmetry, space group P1̄, a = 10.086(1), b = 14.431(2), c = 14.911(2) Å, α = 79.13(1), β = 74.943(9), γ = 88.33(1)°, V = 2058.0(4) Å3, Z = 2. The crystal structure consists of isolated fullerene and silane molecules. At -80°C, C60 is still rotationally disordered. Temperature dependent Guinier powder diagrams do not show any phase transformation between 25 and -165°C. The compound is stable in air.
Enantioselektive Katalyse, XVIII Der Einfluß nicht koordinierter Stereozentren auf die enantioselektive Hydrierung/Enantioselective Catalysis, XVIII The Influence of Non-Coordinated Stereocenters on the Enantioselective Hydrogenation
Authors: Nagel Ulrich , Roller Christoph
Published: February 2015

3,4-Bis{[2-(methyl-phenyl-oxophosphanyl)-ethyl]phenyl-phosphanyl}pyrrolidines have be­en synthesized by Michael Addition from the corresponding methyl-phenyl-vinyl-phosphane oxides and 3,4-bis(phenylphosphino)pyrrolidines. For purification of the ligands palladium complexes were used and with the enantiomerically pure ligands Rh complexes have been pre­pared. The catalyst has 6 stereogenic centers. In the hydrogenation of Z-α-acetamidocinnamic acid all six stereogenic centers have an influence on the enantioselectivity. The influence is strongest from the C stereocenters of the pyrrolidine ring. Less important are the stereogenic centers on the coordinated P atoms. The influence of the stereocenters on the non-coordinated P = O groups is the least, but it is not negligible. The ee values obtained with the ligands containing P = O groups are much lower than those obtained with ligands which are substituted only with aryl groups. Ketones are hydrogenated with only low ee’s.