bluuebunny/crossref_metadata_2025 huggingface dataset:
Derivate des Hydrazins als Liganden in Vanadium(III)-, -(IV)- und -(V)-Komplexen. Darstellung und Charakterisierung von [V(dipic)(NH2NHCOPh)(H2O)2][VO(dipic)(NHNCOPh)]·2H2O , [VO(dipic) (NHNHCO2Me)], [VO(dipic)(NH2NHCO2Me)], [VO(dipic)(NHNHCSPh)] und [VO('ONO')(NHNHCOPh)]·2H2O / Substituted Hydrazines as Ligands in Vanadium(III), -(IV) and -(V) Complexes. Synthesis and Characterization of [V(dipic)(NH2NHCOPh)(H2O)2][VO(dipic)(NHNCOPh)]·2H2O , [VO(dipic) (NHNHCO2Me)], [VO(dipic)(NH2NHCO2Me)], [VO(dipic)(NHNHCSPh)] und [VO('ONO')(NHNHCOPh)]·2H2O
Authors: Sundheim Angelika , Theers Christiane , Mattes Rainer
Published: February 2015

The reaction of [VO(dipic)(H2O)2]·2H2O with benzoylhydrazine, thiobenzoylhydrazine and O-methylcarbazate yields [V(dipic)(NH2NHCOPh)(H2O)2][VO(dipic)(NHNCOPh)·2H2O (1), [V0(dipic)(NHNHCO2Me)] (2), [VO(dipic)(NH2NHCO2Me)] (3) and [VO(dipic)(NHNHCSPh)] (4). 1 is probably formed in solution by redox disproportionation. The reactions giving 2,3 and 4 also involve redox processes with atmospheric oxygen as oxidant and the respective hydrazine as reductant. [VO('ONO')(NHNHCOPh)]·H2O (5) was formed using aqua-oxo-salicylaldehyde-L-alaninato-vanadium(IV) as precursor. The structures of 1,2,3 and 5 have been determined by single crystal X-ray crystallography.

The cation of 1 has a seven-coordinated vanadium(III) center with the two H2O molecules at the apices of a pentagonal bipyramide, the anion contains the doubly deprotonated hydrazido( 2-) ligand NHNCOPh2- as N,O-chelate. 2 and 3 have very similar structures, but differ in the oxidation state of the vanadium atom and in the degree of deprotonation of the hydrazine. In 3 neutral NH2NHCOOMe and in 2 the single deprotonated hydrazido(l -) ligand NHNHCOOMe- are bound as N,O-chelates, with the O-donor in rrans-position to the VO group. The remaining coordination sites are occupied by the ONO-donating dinegative dipic ligand. 5, where dipic is replaced by the three-dentate salicylaldehyde-benzoyl-hydrazone, has a very similar structure to 2. 4 with a VO3N2S coordination sphere is the first vanadiun (V) complex containing the N,S-donating hydrazido(l-) ligand NHNHCSPh-. The following parameters are characteristic for the bonding of the NHNHR- and NHNR2- ligands in 1,2 and 5: V-N 189 ± 1 pm, N-N 134 ± 1 pm and V-N-N 122 ± 2°.
Lithium-zinkate mit heteroleptischem Triorganylzinkat-Anion / Lithium Zincates with Heteroleptic Triorganylzincate Anion
Authors: Westerhausen Matthias , Rademacher Bernd , Schwarz Wolfgang , Henkel Sonja
Published: February 2015

Bis[bis(trimethylsilyl)methyl]-as well as bis(2,2,4,4,6,6-hexa-methyl-2,4,6-trisila-cyclo-hexyl)zinc react with methyl lithium or phenyl lithium in the pres­ ence of the tridentate l,3,5-trimethyl-l,3,5-triazinane (TMTA) to yield zincates of the type LiZnR2R'·2TMTA. The compounds are colorless and insoluble in aliphatic or aromatic hydrocarbons. These zincates exist in solution as well as in the crystalline state as separated ions, as confirmed for lithium-methyl-bis(2,2,4,4,6,6-hexamethyl-2,4,6-trisila-cyc/o-hexyl)-zincate · 2TMTA by X-ray diffraction (P1̄; a -1139,5(3); b = 1482,4(4); c = 1528,6(5) pm; α = 95,33(2); β = 100,13(2); γ = 106,91(2)°; Z = 2). The lithium cation is six-coordinated by two TMTA ligands in a distorted anti-prismatic complex. The zinc atom displays a trigonal planar coordination with Zn-C bond lengths of 207 pm to the 2,2,4,4,6,6-hexamethyl-2,4,6-trisila-cyc/o-hexyl ligands and of 202 pm to the methyl group. One trisila-cyc/o-hexyl substi­ tuent exists in the chair, the other one in the twist conformation. The reaction of lithium bis(trimethylsilyl)amide with bis(trimethylsilylmethyl)zinc yields the benzene soluble lithium-bis(trimethylsilyl)amino-bis(trimethylsilylmethyl)zincate TMTA. The molecular structure was confirmed by X-ray diffraction (P212121; a -1024,8(3); b = 1775,4(7), c = 1918,2(8) pm; Z = 4). The bridging bis(trimethylsilyl)amino ligand displays long Zn-N and Li-N distances of 213 and 208 pm, respectively, due to the steric inter-ligand repulsion. During the reaction of lithium bis(trimethylsilyl)amide with bis[bis(trimethylsilyl)methyl]-zinc no zincate formations observed. The decomposition products lithium bis(trimethylsilyl)-methanide and the heteroleptic bis(trimethylsilyl)amino-bis(trimethylsilyl)methylzinc were detected.
Crystal Structure of trans-Bis(acetonitrile)dich]oroplatinum(II)
Authors: Kritzenberger Jürgen , Yersin Hartmut , Range Klaus-Jürgen
Published: February 2015

We have determined the crystal and molecular structure of trans-bis(acetonitrile)dichloroplatinum(II). Crystallographic data for trans-Pt(CH3CN)2Cl2: monoclinic, space group P21/c, a = 5.0453(9), b = 6.9896(5), c = 11.962(1) Å , β = 101.40(1)°, V = 413.5 Å3, Z = 2 ,Dx = 2.796 g cm-3,μ(CuKα) = 377.5 cm-1, R = 0.0502, wR = 0.0529 for 43 variables and 807 reflections with F > 3σ(F). The Pt atom is in a planar configuration with N and Cl atoms in trans positions. The shortest distance between two Pt atoms corresponds to the length of the crystallographic a-axis (5.045 Å). Additionally, we present optical absorption data of the cis-and trans-isomer.
Phosphaniminato-Cluster des Kupfers. Synthese und Kristallstrukturen von [Cu6Cl6(NPMe3)4]Cl[Me3SiNPMe3] · CH2Cl2 und [Cu6Cl6(NPMe3)4][Cu(Me3SiNPMe3)2]Cl2 / Phosphoraneim inato Clusters of Copper. Syntheses and Crystal Structures of [Cu6Cl6(NPMe3)4]Cl[Me3SiNPMe3] · CH2Cl2 and [Cu6Cl6(NPMe3)4][Cu(Me3SiNPMe3)2]Cl2
Authors: Köcker Rolf Meyer zu , Behrendt Andreas , Dehnicke Kurt , Fenske Dieter
Published: February 2015

The title compounds have been prepared as black-blue crystals with metallic lustre by the reaction of CuCl2 and CuCl, respectively, with Me3SiNPMe3 in CH2Cl2 suspensions. The complexes have been characterized by cyclic voltammetry and by crystal structure determinations.

[Cu6Cl6(NPMe3)4]Cl[Me3SiNPMe3] · CH2Cl2: Space group P212121, Z = 4, structure solution with 4407 unique observed reflections, R = 0.057. Lattice dimensions at -70 °C: a -1159.3(8), b = 2027.1(14), c = 2063.3(12) pm. The compound consists of cluster ions [Cu6Cl6(NPMe3)4]+, in which the copper atoms form a regular octahedron. Four planes of the octahedra are capped by μ3-nitrogen atoms of the (NPMe3)- groups. Each of the Cu atoms is connected with a terminal chlorine atom . Another chloride ion serves for charge compensation; this ion occupies another Cu3 plane of the octahedron. Without bonding interaction one Me3SiNPMe3 molecule and one CH2Cl2 molecule are included in the lattice.

[Cu6Cl6(NPMe3)4][Cu(Me3SiNPMe3)2]Cl2: Space group Pna21, Z = 4, structure solution with 5676 unique observed reflections, R = 0.071. Lattice dimensions at -70 °C: a = 3117.2(21), b = 1927.4(11), c = 1002.7(8) pm. The compound consists of cluster ions [Cu6Cl6(NPMe3)4]+, the complex ion [Cu(Me3SiNPMe3)2]+, and chloride ions. In the cation [Cu(Me3SiNPMe3)2]+ the copper atom is linearly coordinated by the nitrogen atoms of the phosphaneimine molecules.
Phasendiagramme und Exzeßvolumina der Systeme (CH3)2SiCl2/Pyridin und (CH3)2CCl2/Pyridin / Phase Diagrams and Excess Volumes of the Systems (CH3)2SiCl2/Pyridine and (CH3)2CCl2/Pyridine
Authors: Zenke Michael W. , Hensen Karl
Published: February 2015

The isobaric melting and boiling diagrams for the systems: dimethyldichlorosilane/pyridine and 2,2-dichloropropane/pyridine are reproduced. The existence of the incongruently melting addition compounds (CH3)2SiCl2 · (Pyridine)2 and [(CH3)2CCl2]3 · Pyridine could be proved. Some measurements of the molar volume of mixtures of pyridine and dimethyldichlorosilane, and pyridine and 2,2-dichloropropane are reported. For both systems the molar excess volume has been calculated as a function of the mole fractions.
Die Röntgenstrukturanalyse der Pyrrolide (CH3)2Al - C4H3NCH3 und (CH3)2Ga - N(CCH3)4 / The X-Ray Structure Determination of the Pyrrolides (CH3)2Al - C4H3NCH3 and (CH3)2Ga - N(CCH3)4
Authors: Hausen Hans-Dieter , Tödtmann Jochen , Weidlein Johann
Published: February 2015

N-M ethyl-2-dimethylaluminium pyrrolide, (CH3)2Al -C4H3NCH3, crystallizes in the triclinic space group P1̄ with the lattice constants a = 700.5(1), b = 725.9(1), c = 886.8(1) pm, α = 67.69(1)°, β = 70.99(1)°, γ = 88.48(1)°, and Z = 2. This compound is isotypic with the gallium homologue [1], the shortest metal-ring contact between the two molecules of one unit cell decreases to 228.6 pm. N-dimethylgallium tetramethylpyrrolide has been synthesized from Li-N (CCH3)4 and (CH3)2GaCl. This “π-associate” crystallizes in the monoclinic space group P21/c with the lattice parameters a = 989.9(2), b = 1305.4(3), c = 878.3(2) pm, β - 112.73(1)° and 4 units per cell. Again two centrosymmetrically orientated molecules form a dimer by short (224.0 pm) intermolecular “Ga - πC ” contacts but the structure differs significant from the structure of the indium homologue [1].
Neue Borkohlenstoffheterocyclen: Benzo-1,4-diboracyclohepten-2, 1,4-Diboracyclohepten-2 und das isomere 6.6-Dimethy 1-2-methyliden-1,3-diboracyclohexan / New Organoboran Heterocycles: Benzo-1,4-diboracycloheptene-2, 1,4-Diboracyclopentene-2 and the Isomeric 6,6-Dimethyl-2-methylidene-1,3-diboracyclohexane
Authors: Schulz H. , Seyffer H. , Deobald B. , Pritzkow H. , Siebert W.
Published: February 2015

The reaction of 1,1-bis(trim ethylstannyl)-2-m ethylpropene-1 and 1,3-bis(dichloroboryl)- propane leads to the chloro derivate of 6,6-dimethyl-2-m ethylidene-1,3-diboracyclohexane (1a), in which the Cl atoms are substituted by the dimethylamino and the methyl group to yield lb and 1c . Similarly the benzo-1,4-diboracycloheptene-2 derivative 2a is obtained from 1,2-C6H4(SnMe3)2 and (Cl2B)2C3H6. Replacement of the substituent leads to the dimethylamino (2b) and methyl derivatives (2c). Redox reaction between hexyne-3 and (I2B)2C3H6 results in the formation of 1,4-diiodo-2,3-diethyl-1,4-diboracycloheptene-2 (3a), which is methylated to give 3c. The constitutions of 1a-c, 2a-c and 3a,c are derived from NMR and MS data and are confirmed by X-ray structure analyses for 1b and 2b.
Transition Metal Pnictide Synthesis: Self Propagating Reactions Involving Sodium Arsenide, Antimonide and Bismuthide
Authors: Hector Andrew L. , Parkin Ivan P.
Published: February 2015

Initiation of the reaction between Na 3E (E = As, Sb, Bi) and anhydrous metal halides at 25 to 550 °C produces metal arsenides MxAsy (M=Y,La, Ti, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Pt ,Cu and Zn) and antimonides MxSby (M=Ti, V, Nb, Ta, Cr, Fe, Co, Ni, Pt, Cu and Zn) via an exothermic selfpropagating reaction. The metal arsenides were characterized by X-ray powder diffraction, SEM/EDAX , microanalysis and FT-IR.
Darstellung und Kristallstruktur des Bis(trimethylammonium)hexasulflds [HN(CH3)3]2S6 / Preparation and Crystal Structure of Bis(trimethylammonium)hexasulfide [HN(CH3)3]2S6
Authors: Müller C. , Böttcher P.
Published: February 2015

The reaction of trimethylamine, H2S, and sulfur in ethanol yields orange crystals of bis(trimethylammonium) hexasulfide. The com pound crystallizes in the centrosymmetric monoclinic space group P 2/c. The lattice constants are a = 10.310(7), b = 5.752(2), c = 13.348(10) Å, β = 98.41(6)°. The S2
6-chain has a helical all-trans-conformation (sequence of the signs of torsion angles +++ and --- ).
Crystal and Molecular Structure of Aminoguanidine Sulphate, an Important Enzyme Inhibitor and Starting Material of Drug Syntheses
Authors: Koskinen Mikko , Mutikainen Ilpo , Elo Hannu
Published: February 2015

Aminoguanidine is not only an agent with a variety of pharmacological effects but also an important starting material of am idinohydrazone-type drugs and enzyme inhibitors. There­ fore, we have now synthesized am inoguanidine sulphate CN4H8
2+.SO4
2- and determined its structure by single-crystal X-ray diffraction. The doubly protonated (dication) form of amino­ guanidine that is present in the sulphate could, in principle, exist in the form of several different tautom ers. The crystal studied consisted exclusively of one tautomer: one of the nitrogens of the hydrazine moiety bears three hydrogen atoms while the other one (the one bound to the carbon) bears one hydrogen. The other two nitrogens are bound to two hydrogens each. The predominance of this tautomer can be explained by the very strong resonance in it. The dication of aminoguanidine is remarkably planar. The hydrogens of the hydrazine moeity are, however, clearly out of the plane of the other atoms. There is a strong hydrogen bond between the proton of the m onoprotonated nitrogen and one sulphate oxygen. This bond obviously causes the deviation of the hydrogen from the plane. The bonds between the carbon atom and the adjecnt nitrogens are essentially equally long, indicating that each bond has approximately the same amount of double bond character. One of the positive charges of the dication is thus delocalized, being shared by all of the atoms of the CN3 moiety. In this respect, the structure is similar to that of all bis(amidinohydrazones) whose structures have been determined. The other positive charge of aminoguanidine dication is localized at the nitrogen bearing three hydrogens.
Crystal Structure of Sr0.2Ca2.8Tl2O6
Authors: Ruck Kirsten , Borrmann Horst , Simon Arndt
Published: February 2015

The crystal structure of Sr0.2Ca2.8Tl2O6 has been determined by single crystal X-ray diffraction. The compound crystallizes in space group Pbam (No. 55) with a = 11.228(1), b = 16.471(1) and c = 3.3326(3) Å. It is isostructural with Ca3In2O6 and SrCa2In2O6.
Das Anion [R2Al-AlR2Br]- (R = CH(SiMe3)2) mit Aluminium-Aluminium- und terminaler Aluminium-Brom-Bindung / The Anion [R2Al-AlR2Br]- (R = CH(SiMe3)2) with an Aluminium -Aluminium and a Terminal Aluminium -Bromine Bond
Authors: Uhl Werner , Schütz Uwe , Pohl Siegfried , Saak Wolfgang
Published: February 2015

Tetrakis[bis(trimethylsilyl)methyl]dialane(4) (1) with an Al-Al bond reacts with LiBr in n-pentane in the presence of chelating N.N.N'.N'-tetramethylethylenediamine (TMEDA) to yield the monobromo adduct [Li(TMEDA)2]+[R2Al-AlR2Br]- 4. Compound 4 is unstable in ethereal solution and decomposes with quantitative formation of LiBr and the starting compound 1. Crystal structure determination of 4 C5H10 shows a terminal Al-Br bond in an anion with a four-coordinated aluminium atom neighbouring a three-coordinated, coordinatively unsaturated aluminium atom. While the Al-Al bond length is not significantly different (264.3 pm) as compared to the data for 1, the Al-Br bond is rather long (247.6 pm) indicating a weak coordinative bonding.
A New Synthesis of Dimethylgold(III) Chloride Using Tetramethyltin
Authors: Paul Martin , Schmidbaur Hubert
Published: February 2015

The reaction of HAuCl4 or AuCl3 with Sn(CH3)4 in methanol at low temperatures gives [(CH3)2AuCl]2 in yields from 40 to 45%.
Synthesis and Characterization of Cu(II) and Mono-and Dinuclear Pb(II) Complexes Derived from 3,5-Diacetyl-1,2,4-triazole
Authors: Souza P. , Matesanz A. I. , Arquero A. , Fernandez V.
Published: February 2015

Template 1:1 condensation of 3,5-diacetyl-1,2,4-triazole with thiocarbohydrazide or car- bohydrazide in the presence of 1 equivalent of Pb(SCN)2 produces mononuclear [2 + 1] com­plexes 1 and 3. The analogous reaction with thiosemicarbazide and semicarbazide produces the dinuclear [1+2] complex 2 and the mononuclear metal free 4. The carbohydrazide deriva­tive 3 reacts with the carbohydrazide or the 1,3-diaminopropane to yield the macrocyclic dinuclear complexes 5 and 6.

Direct reaction of 3,5-diacetyl-1,2,4-triazole with thiocarbohydrazide. carbohydrazide, thiosemicarbazide and semicarbazide leads to open [1+1] ligands L1, L2, L3, L4, and closed [1+1] ligands (mesocyclic ligands) L5 and L6 were prepared by addition of 1 equivalent of LiOH to the reaction mixture.

The reaction of open and mesocyclic [1+1] ligands with copper(II) salts gives [CuLX2] and [Cu2+L2-] complexes. All these compounds have been characterized by 1H NMR, IR, electronic and mass spectra and by analytical data.
Bildung von Iodoantimonaten und -bismutaten. Kristallstrukturen von (PhCH2NEt3)4[Sb6I22], (PhCH2NEt3)4[Bi6I22] und (Ph4P)3[Bi5I18] / Formation of iodoantim onates and bismutates. crystal structures of (PhCH2NEt3)4[Sb6I22], (PhCH2NEt3)4[Bi6I22] and (Ph4P)3[Bi5I18]
Authors: Pohl Siegfried , Peters Michael , Haase Detlev , Saak Wolfgang
Published: February 2015

The formation and the crystal structures of the title compounds are reported. (PhCH2NEt3)4[Sb6l22] and (PhCH2NEt3)4[Bi6I22] are isotypic and contain a novel [E6I22]4- anion (E = Sb, Bi). The anion of (Ph4P)3[Bi5I18] consists of a linear chain of five face-sharing [Bil6] octahedra
Thermodynamische Untersuchungen zur Lewis-Acidität von Trimethylchlorsilan - die Phasendiagramme und Exzeßvolumina der Systeme (CH3)3SiCl/Pyridin und (CH3)3CCl/Pyridin / Thermodynamic Examinations on the Lewis Acidity of Trimethylchlorosilane - the Phase Diagrams and Excess Volumes of the Systems (CH3)3SiCl/Pyridin and (CH3)3CCl/Pyridin
Authors: Zenke Michael W. , Hensen Karl
Published: February 2015

The isobaric melting and boiling diagrams for the systems: trimethylchlorosilane/pyridine and trimethylchloromethane/pyridine are reproduced. Some measurements of the molar volume of mixtures between trimethylchlorosilane and pyridine and trimethylchloromethane and pyridine are reported. For both systems the molar excess volume has been calculated as a function of the mole fractions
Über ein gemischtvalentes Oxoniobat mit planaren Polygonen um Niob und Barium: BaNb2+Nb2
4+O6 / On a Mixed Valent Oxoniobate Containing Planar Polygons Around Niobium and Barium: BaNb2+Nb2
4+O6
Authors: Möhr S. , Müller-Buschbaum
Published: February 2015

Single crystals of BaNb3O6 were prepared by CO2-LASER high temperature technique. The compound crystallizes with trigonal symmetry C5
3v-R3m , a = 11.4333, c = 3.4949 Å , Z = 3. The new structure type is characterized by planar NbO4 and planar BaO6 polygons. The results are discussed with respect to related compounds like Ca0.75Nb3O6 or NaNb3O6.
Zur Kenntnis von EuBeGd2O5 mit einem Beitrag über Phasen der Zusammensetzung M1-xM′xBeLn2O5: Ca0,4Sr0,6BeSm2O5, Ba0,25Ca0,75BeNd2O5 und Ba0,36Sr0,64BeNd2O5 / On EuBeGd2O5 and on Phases of the Composition M1-xM′xBeLn2O5: Ca0,4Sr0,6BeSm2O5, Ba0,25Ca0,75BeNd2O5 and Ba0,36Sr0,64BeNd2O5
Authors: Müller-Buschbaum Hk. , Frenzen S.
Published: February 2015

Single crystals of (I): EuBeGd2O5, (II): Ca0,4Sr0,6BeSm2O5, (III): Ba0,25Ca0,75BeNd2O5 and (IV): Ba0.36Sr0.64BeNd2O5 were prepared by (I): plasma torch and (II)-(IV ): CO2-LASER technique. X-Rayo investigations lead to (I) monoclinic (space group C5
2h-P21/c, a = 7.126, b = 6.457, c = 9.394 Å , β = 90.40°) and (II)-(IV) orthorhombic symmetry (D16
2h-Pnma). (II: a = 9.454, b = 7.142, c = 6.490 Å; III: a = 9.508, b = 7.188, c = 6.531 Å; IV: a = 9.642, b = 7.295, c = 6.614 Å). In contrary to the phases M1-xM′xBeLn2O5, EuBeGd2O5 is characterized by an ordered distribution of Eu2+ and Gd3+ inside of the Kagomé network.
Studies on Bis-hydrazine Complexes of Metal Propionates and Mixed Metal Propionates
Authors: Sivasankar B. N. , Govindarajan S.
Published: February 2015

Metal propionate hydrazinates, M(CH3Ch2COO)2(N2H4)2 where M = Mn, Co, Ni, Zn or Cd, and mixed metal propionate hydrazinates with cobalt, M1/3Co2/3(CH3CH2COO)2(N2H4)2 where M = Mg, Mn, Ni, Zn or Cd, have been prepared and characterized by analytical, magnetic, spectral, thermal and X-ray diffraction studies. The thermal decomposition of the former complexes yields the metal oxides while the latter mixed metal complexes give the corresponding metal cobaltites as the final residue. Formation of metal cobaltites has been confirmed by TG weight loss, IR spectra and X-ray diffraction.
Wechselwirkungen in Kristallen, 35 [ 1, 2] Einkristallzüchtung von Na⊕⊖C(NO2)3 [***] aus Etherlösungen zu einem polymeren Band [(Na⊕⊖C(NO2)3) Dioxan]∞ und einem Lösungsmittel-getrennten Ionenpaar [(Na⊕/18-Krone-6)(THF)2]⊕ [(Na⊕/18-Krone-6)(ONO-C⊖(NO2)2)2]⊖ / Interactions in Crystals, 35 [1, 2] Single Crystal Growths of Na⊕⊖C(NO2)3[***] from Ether Solutions to a Polymer Band [(Na⊕⊖C(NO2)3)Dioxane]∞ and to a Solvent-Separated Ion Pair [(Na⊕/18-Crown-6)(THF)2]⊕[(Na⊕/18-Crown-6)(ONO-C
⊖
(NO2)2)2]⊖
Authors: Bock H. , Hauck T. , Näther C. , Havlas Z.
Published: February 2015

The sodium salt of the most simple polynitro-substituted hydrocarbon anion. Na⊕⊖C(NO2)3, (for a hazard warning cf. [***]) crystallizes from ether solutions without and with addition of 18-crown-6 either in a polymer band. [(Na⊕⊖C(NO2)3)dioxane]∞, or as a solvent- separated ion pair, [(Na⊕/18-crown-6)(THF2]⊕[(Na⊕/18-crown-6)(O2N-C⊖(NO2)2)2]⊖. The Na⊕ cations are each 8-fold coordinated in hexagonal bipyramidal arrangement. According to extensive quantum-chemical calculations based on the structure coordinates, the formation of these novel salts can be traced back to the charge distribution in the anions ⊖C(NO2)3. which due to negatively charged oxygen centers are favorable complex ligands. The structure determining effects of solvation are discussed.
A Novel Synthetic Approach to Asymmetric Salen, Dihydrosalen, and Tetrahydrosalen Ligands: Structures and O2-Activating Properties of their Nickel(II) and Cobalt(II) Complexes
Authors: Böttcher Arnd , Elias Horst , Eisenmann Brigitte , Hilms Elke , Huber Andreas , Kniep Rüdiger , Röhr Caroline , Zehnder Margareta , Neuburger Markus , Springborg Johan
Published: February 2015

A synthetic procedure is described for the preparation of the tetradentate N2O2 ligands H2[H4]L1=6-(2-hydroxyphenyl)-2,5-diaza-3,3-dimethyl-1-(2-hydroxy-3-t-butyl-5-methyl- phenyl)heptane, H2[H2]L1 = 6-(2-hydroxyphenyl)-2,5-diaza-3,3-dimethyl-1-(2-hydroxy-3-t-butyl-5-methylphenyl)-1-heptene, and H2L1 = 6-(2-hydroxyphenyl)-2,5-diaza-3,3-dimethyl-1-(2- hydroxy-3-t-butyl-5-methylphenyl)-1,5-heptadiene, which are asymmetric derivatives of the ligands tetrahydrosalen, dihydrosalen, and salen. Complexes Ni[H4]L1, Ni[H2]L1, NiL1, CoL1, Ni[H4]L2 (([H4]L2)2- = anion of H2[H4]L2 = N,N'-bis(2-hydroxy-3-t-butyl-5-methylbenzyl)- trans-(S,S)-1,2-diaminocyclohexane), and NiL2 were prepared, characterized (VIS and IR ab­sorption, magnetic moment) and subjected to spectrophotometric titration with pyridine, to determine the equilibrium constants for adduct formation. Single crystal X-ray structure analy­ses were carried out for Ni[H2]L1 (monoclinic, P21/n; a = 8.926(4), b = 29.324(7), c = 8.411(4) Å; β = 95.3(1)°; Z = 4), CoL1 (monoclinic, C2/c; a = 25.389(2), b = 18.139(2), c = 10.179(1) Å; β = 112.227(6); Z = 8), and Ni[H4]L2·acetone (tetragonal, P41212; a = 13.928(3), c = 33.698(5) Å; Z = 8). In all of the three complexes, the N2O2-metal coordination core is square-planar. The skeleton of the tetradentate ligand is more or less twisted. The planar cobalt(II) complex CoL1 is a low spin d7 system with μexp = 2.02 BM at 298 K, whereas the planar complexes NiL1, Ni[H2]L1 and Ni[H4]L2 are diamagnetic (μexp = 0.28-0.64 BM). The blue solvate Ni[H4]L1- 3EtOH · H2O is paramagnetic (μexp = 3.04 BM), which points to octahedral coordination. In aerated acetone solution, the tetrahydrosalen-type complex Ni[H4]L1 activates dioxygen and one C-N bond is oxidatively dehydrogenated. The VIS spectrum of the dihydrosalen-type complex formed is virtually identical with that of the aldimine complex Ni[H2]L1. In the pres­ence of dioxygen, Co[H4]L1 and Co[H2]L1 are readily oxidized to CoL1 in acetone solution.
Eine effiziente Synthesemethode für DiarylallenyIiden(pentacarbonyl)chrom- und -wolfram-Komplexe -Kristallstruktur von (CO)5Cr=C=C=CPh2 / An efficient Synthesis of Diarylallenylidene Pentacarbonyl Chromium and Tungsten Complexes - Crystal Structure of (CO)5Cr=C=C=CPh2
Authors: Fischer Helmut , Reindl David , Roth Gerhard
Published: February 2015

An efficient synthesis of diarylallenylidene pentacarbonyl chromium and tungsten com­plexes is presented. Irradiation of M(CO)6 in THF affords (CO)sM[THF], Substitution of the THF ligand by diarylpropargylalcoholate and subsequent desoxygenation with COCF gives the title compounds in good yield. (The structure of diphenylallenylidene pentacarbonyl chromium has been determined by X-ray structure analysis
Structure and Magnetic Properties of a Dinuclear Complex with Iron(III) in Octahedral and Pyramidal Coordination
Authors: Elmali Ayhan , Elerman Yalcin , Svoboda Ingrid , Fuess Hartmut , Griesar Klaus , Haase Wolfgang
Published: February 2015

[FeL(MeOH)Cl]2 (L = N-(2-hydroxyphenyl)salicylaldimine) was synthesized and its crystal structure determined, [C27H20N 2O5Cl2Fe2], monoclinic, space group P21/c, a = 9.528(1), b = 7.684(1), c = 18.365(2) Å, β = 109.83(1)°, V = 1264.8 Å3, Z = 2. Two identical [FeL(MeOH)Cl] fragments, related by an inversion centre, are combined by the two bridging O atoms, to form a binuclear unit. The iron(III) centers are separated by 3.163(2) Å and weakly antiferromagnetically coupled (J = -8 .0 (1 ) cm-1), which follows from temperature - dependent magnetic susceptibility measurements in the range 4.2 to 288 K. The effective magnetic moment per iron(III) is μeff = 7.4 μB at 288 K
Metallkomplexe 6,6′-Dialkinyl-substituierter 2,2′-Bipyridin-Liganden: Synthese und Struktur von [{6,6′-(CH3CH2CH2C = C)2bpy}Cu(Cl)(µ-Cl)]2 / Metal Complexes of 6,6′-Dialkynyl-Substituted 2,2′-Bipyridine Ligands: Synthesis and Structure of [{6,6′-(CH3CH2CH2C = C)2bpy}Cu(Cl)(µ-Cl)]2
Authors: Kövári Endre , Krämer Roland
Published: February 2015

The bipyridyldiacetylene 6,6′-(CH3CH2CH2C = C)2bpy (1) was prepared by palladium catalyzed C - C - coupling reaction of 6,6′-dibromo-2,2′-bipyridine with pentyne. Reaction of 1 with anhydrous CuCl2 in acetonitrile gave the dimeric, chloro-bridged complex (1)Cu(Cl)(µ-Cl)2Cu(Cl)(1) (2), which was characterized by X-ray crystallography. The copper atoms in 2 are square-pyramidally coordinated with normal in-plane Cu - N and Cu - Cl bond distances and one longer, apical bond to the second bipyridyl nitrogen atom. The influence of steric hindrance of the bipyridyl 6,6′-substituents on the structure of the complex is discussed.
Zur Kristallstruktur der Cyanoelpasolithe [N(CH3)4]2CsCo(CN)6 und [H3NCH3]2NaFe(CN)6 / Concerning the Crystal Structures of the Cyano-Elpasolites [N(CH3)4]2CsCo(CN)6 and [H3NCH3]2NaFe(CN)6
Authors: Peschel Stefan , Babel Dietrich
Published: February 2015

Single crystals of the cyano complexes [N(CH3)4]2CsCo(CN)6 and [H3NCH3]2NaFe(CN)6 were prepared and their structures determined by X-ray methods. The cobalt compound is monoclinic, a =885.5(1), b = 892.6(2), c = 1259.9(5) pm, β = 90.29(4)°, space group I2/m, Z = 2; R1 = 0.048 for 861 independent reflections. The resulting average distances in the nearly undistorted octahedra are Co - C = 189.8, C - N = 114.1, Cs - N = 325.6 pm. The iron compound exhibits a cubic elpasolite type structure, a = 1105.2(1) pm, space group Fm 3m , Z = 4; R1 = 0.040 for 127 independent reflections; Fe - C = 193.4(6), Na - N = 247.7(8) pm. The orientation of the librating tetramethyl-ammonium group within the cages of the cobalt compound and the disorder of the monomethyl-ammonium cation around the special site (1/4, 1/4, 1/4) of the iron complex are discussed.
Determination of Absolute Signs of 119Sn-117Sn Spin-Spin Coupling Constants
Authors: Wrackmeyer Bernd , Kehr Gerald
Published: February 2015

If for a given system two-dimensional (2D) 119Sn/1H heteronuclear shift correlations can be established for long range coupling constants nJ(119Sn,1H) (n = 4, 6), absolute signs of coupling constants J(Sn,Sn) are accessible by this technique for the first time. This has been demonstrated for tetrakis(trimethylstannyl)allene (1) with 2J(119Sn,117Sn) (>0) and 4J(Sn. 117Sn) (<0) and for tris(trimethylstannyl)phosphane (2) and bis(trimethvlstannyl)- sulfane (3) with 2J(119Sn,117Sn) (<0).
Ternary Rare Earth Metal Gold Stannides and Indides with Ordered U3Si2 and Zr3Al2-Type Structure
Authors: Pöttgen Rainer
Published: February 2015

The new ternary stannides RE2Au2Sn (RE = Gd, Tb) and indides RE2Au2In (RE = Y, Gd-Tm, Lu) were synthesized by arc-melting of the elemental components and subsequent annealing at 800 °C. While Gd2Au2Sn, Tb2Au2Sn and the indides with RE = Y, Gd-Er crystallize in the ordered U3Si2 structure, Tm2Au2In and Lu2Au2In adopt the ordered Zr3Al2 structure, respectively. The crystal structure of Dy2Au2In was refined from single-crystal X- ray data: P4/mbm, Z = 2, a = 784.1(1) pm, c = 373.9(1) pm, V = 0.2299 nm3 and R = 0.028 for 342 F2 values and 12 variables. The tin (indium) atoms in these compounds occupy [RE8] square prisms and the gold atoms are surrounded by [RE6] trigonal prisms. These fragments are derived from the AlB2 and CsCl-type structures. The crystal chemistry of these com­pounds is briefly discussed.
Organometallic Rhodium(III) and -(I) Complexes with 1,3-Diniethyllumazine(DML). The Crystal Structure of [(η2- (O4,N5)DML)(η5-C5Me5)ClRh](PF6)
Authors: Heilmann Oliver , Hausen Hans-Dieter , Kaim Wolfgang
Published: February 2015

The crystal structure determination of the new rhodium(III)-complex [(DML)(C5Me5)ClRh](PF6). DML = 1,3-dimethyllumazine, reveals O4,N5 coordination of the metal to DML with not very different bond lengths of 213.0(2) pm (Rh-N) and 219.2(2) pm (Rh-O). This result stands in contrast to the previously reported structure of a cationic dihydrobiopterin bound to [Mo(O)Cl3]- which exhibited a very unsymmetrical chelate ar­rangement. Chemical and electrochemical two-electron reduction of the Rh(III) complex led to a very labile Rh(I) species (DML)(C5Me5)Rh which is distinguished by an intense charge transfer band in the visible. The results confirm the characterization of DML as a weak σ donor/π acceptor ligand with a rather low-lying π* orbital.
Einfache photochemische Synthese von Benzylphosphanen / Facile Photochemical Synthesis of Benzylphosphines
Authors: Müller Gerhard , Waldkircher Martin , Winkler Martin
Published: February 2015

Facile large-scale synthesis of the benzyl-dibromo-phosphines RPBr2 (R = C6H5CH2, 3,5-Me2C6H3CH2, 2-BrC6H4CH2) is accomplished by the photochemical reaction of toluene, mesitylene, and 2-bromotoluene, respectively, with PBr3 in the absence of solvent. If the reactions are carried out up to 50% completion the amount of by-products formed is remark­ ably low, rarely exceeding 10% of the total amount of products formed. The selectivity of the photoreaction may be improved up to 98% if it is carried out in a modified Soxhlet apparatus which allows the predominant irradiation of only the starting materials. The appar­ ent limitations imposed by the low turnovers required to achieve good product selectivity are by far outweighed by the large amounts of desired products formed in a short period of time and by the easy recovery of unreacted starting material by distillation. Thus in the case of 2-BrC6H4CH2PBr2, in a typical run 94 g (261 mmol) of product may be isolated after 2.5 h of irradiation of 970 mmol of 2-BrC6H5CH3 and 1.39 mol of PBr3. In this case the turnover is 32%. the isolated yield 27%, and the by-product 2-methylphenyl-dibromo-phosphine only amounts to less than 2%. The benzyl-dibromo-phosphines are easily methylated with two equivalents of MeMgCl to give the respective benzyl-dimethyl-phosphines in 79-93% yield. Tertiary benzylphosphines MePRR′ (R = 2-BrC6H4CH2, R′ = Me3SiCH2; R = R′ = 2-BrC6H4CH2) are obtained in easy one-pot syntheses by consecutive reactions of 2-BrC6H4CH2PBr2 with Me3SiCH2MgCl and MeMgCl, and with 2-BrC6H4CH2MgBr and MeMgCl, respectively.
Chiral Thioaldehyde Complexes of Rhenium, X-Ray Structure Determination of [Cp(NO)(Ph3P)Re(η2-S=CHPh)]PF6 [1]
Authors: Schenk Wolfdieter A. , Burzlaff Nicolai , Burzlaff Hans
Published: February 2015

Chiral thiolate complexes [Cp(NO)(Ph3P)ReSCH2R] (R=Ph, 4-C6H4Cl, 4-C6H4OMe, H, Me) are obtained from [Cp(NO)(Ph3P)ReCH3] by acid cleavage in the presence of thiol and subsequent deprotonation. Small amounts of (chloromethyl)thioether complexes [Cp(NO)(Ph3P)ReS(CH2Cl)CH2R]BF4 are formed when dichloromethane is used as a sol­ vent in this reaction. Hydride abstraction using [Ph3C]PF6 converts the thiolate complexes into ionic thioaldehyde complexes [Cp(NO)(Ph3P)Re(η2-S=CHR)]PF6. These are obtained as pure (RR,SS)-diastereomers as shown spectroscopically and by X-ray structure determination of [Cp(NO)(Ph3P)Re(η2-S=CHPh)]PF6. Crystals are monoclinic, space group I2/a (No. 15), a = 25.877(3), b = 18.785(2), c = 13.768(1) Å , β = 104.93(1)°, Z -8.
Synthese und Kristallstruktur von Triphenyltelluroniumsulfid / Synthesis and Crystal Structure of Triphenyltelluroniumsulfide
Authors: Wieber Markus , Lang Stefan , Rohse Stefan , Habersack Ralph , Burschka Christian
Published: February 2015

The synthesis of triphenyltelluroniumsulfide (Ph3TeS)4 is described together with a NMR-spectroscopic characterization. The structure of the title compound was determined by single crystal X-ray diffraction. Crystals of triphenyltelluroniumsulfide are triclinic (space group P1) with the cell parameters a = 1178.0(3) pm. b = 1295.8(6) pm. c = 1298.7(4) pm, α = 77.67(3)°, β = 82.18(2)°, γ = 66.00(2)° (V = 1766(1) × 106 pm3) and Z = 2. The compound appears to form a step-like structure of two [Ph3TeS]2 units and crystallizes with two molecules of CH2Cl2 per unit cell.
Phosphazen-Katalyse. Grundlage der Lineartechnologie zur Siliconherstellung / Phosphazene Catalysis. The Basis of L inear Technology for Silicone Production
Authors: Hager Rudolf , Weis Johann
Published: February 2015

The structure of the chlorophosphazenes used as catalyst for the polycondensation of siloxanoles to various high molecular weight silicone polymers in the industrial scale has been determined as [PCl3=N(-PCl2=N)x-PCl3]+[PCl6]-. mainly with x=1 and x=2. For better un­ derstanding of the catalytic mechanism, the reaction behaviour of these ionic phosphazenes with water and siloxanes has been studied. Thereby three further types of phosphazenes have been synthesized: PCl3=N(-PCl2=N)x-PCl2=O,HO-PCl2=N(-PCl2=N)x-PCl2=O and siloxy derivatives of the latter ≡Si-O-PCl2=N(-PCl2=N)x-PCl2=O. Although several P-Cl bonds could be attacked by the nucleophiles, the reactions were found to be extremely selective and the products were obtained in very high yields. Finally relations between phosphazene structure and catalytic activity have been ascertained to find the optimal catalyst structure.
Calorimetrie an Ammoniumyttriumhalogeniden / Calorimetry of Ammonium Yttrium Halides
Authors: Ehrlich S. , Oppermann H. , Hennig C.
Published: February 2015

The heat of solution of all solid phases in the system YX3-NH4X with X = Cl, Br, I in 4n HX was investigated. The enthalpies of formation of the ammonium yttrium halides are derived from the enthalpies of formation of Y X3 and of NH4X and their heats of solution in An HX:

ΔHB
0(NH4Y2Cl7,f,298) = -561,5 ± 1,7 kcal/mol, ΔHB
0((NH4)3 YCl6,f,298) = -474,5 ± 1,3 kcal/mol,

ΔHB
0((NH4)3YBr6,f,298) = -400,8 ± 2,6 kcal/mol, ΔHB
0((NH4)3YI6,f,298) = -291,9 ± 3,0 kcal/mol.
Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalysen von Tetrahalogenooxalatoosmaten (IV), [OsX4(ox)]2-, X = Cl, Br, I / Crystal Structures, Vibrational Spectra and Normal Coordinate Analyses of Tetrahalogenooxalatoosmates (IV), [OsX4(ox)]2-, X = Cl, Br, I
Authors: Preetz W. , Krull A.
Published: February 2015

The crystal structures of [(C5H5N)2CH2][OsCl4(ox)] (monoclinic, space group I2/m, a = 10.260(5), b = 13.841(5), c = 12.273(5) Å, β = 92.050(5)°, Z = 4), [(C5H5N)2CH2][OsBr4(ox)]·H2O(monoclinic, space group P21/n, a = 11.666(3),b = 11.591(5), c = 14.926(2) Å, β = 102.45(2)°, Z = 4) and [P(C6H5)4]2 [OsI4(ox)]·2CH2Cl2 (triclinic, space group P1̄, a = 14.597(2), b = 11.9185(9), c = 22.5624(14) Å, α = 80.284(8), β = 78.903(8), γ = 69.432(8)°, Z = 2) have been determined by single crystal X-ray diffraction analysis. The IR and Raman spectra of the three complexes were measured at room temperature. Using the molecular parameters of the X-ray determinations normal coordinate analyses based on a modified valence force field have been performed and the normal modes of vibration are assigned. With a set of 25 force constants and taking into account the innerligand vibrations a good agreement between observed and calculated frequencies has been achieved. The valence force constants of the X-Os-X axis are fd(OsCl) = 1.77, fd(OsBr) = 1.48, fd(OsI) = 1.0 mdyn/Å, of the X′-Os-O• axes are fd(OsCl′) = 1.88, fd(OsBr′) = 1.6, fd(OsI′) =1.1 mdyn/Å and fd(OsO•) ranges from 2.7 to 2.8 mdyn/Å.
The Phenomenon of Intramolecular Attractive S---O Interactions: Synthesis and Structure of (1,10-Phenanthroline)copper(II) Complexes with Isonitroso-(4-methylthiazol-2-yl)acetamide and Isonitroso-(4-methylthiazol-2-yl)-(benzothiazol-2-yl)methanide
Authors: Domasevitch Konstantin V. , Ponomareva Vera V. , Mokhir Andrey A. , Rusanov Eduard B. , Sieler Joachim , Hoyer Eberhard
Published: February 2015

Isonitroso-(4-methylthiazol-2-yl)acetamide H (L1), isonitroso-(4-methylthiazol-2-yl)(benzo-thiazol-2-yl)methanide H(L2) and their copper(II) complexes of composition [Cu(Phen){L1}(ClO4)] (1) and [Cu(Phen){L2}Cl]*C2H5OH (2) have been prepared. Crystal and molecular structures of the complexes have been determined from X-ray diffractioon data (1: monoclinic, space group P21/c, with a = 11.611(2), b = 10.259(2), c = 17.869(4) Å, β = 104.67(3)°, V = 2059.1(7) Å3, Z = 4; R1 = 0.046 for the 2522 unique reflections with I > 2σ(I). 2: triclinic, space group P1̄, with a = 8.351(1), b = 10.876(1), c = 14.891(2) Å, a = 96.170(8)°, β = 94.201(9)°, γ = 106.721(9)°, V = 1280.1(2) Å3, Z = 2; R1 = 0.034 for the 4038 unique reflections with I > 2σ(I)). In the structure of 1 the coordination polyhedron of Cu2+ is a distorted square pyramid with an oxygen atom of the CIO4 counter anion in the apex (C u -O 2.505(3) Å); in complex 2 the copper atom adopts fivefold coordination of a slightly distorted trigonal-bipyramidal geometry with a chlorine atom in the equatorial plane (Cu-Cl 2.3504(9) A). Ethanol of crystallization gives rise to a hydrogen bond at the chlorine atom. In both structures the oximic anions are coordinated to the metal center in a bidentate chelate manner via the nitrogen atom of the nitroso group and the carbonyl oxygen atom (1) or via the benzothiazole nitrogen atom (2) (Cu-O, Cu-N in the range 1.963(2) -2.031 (2) Å). The thiazole group of the ligands takes no part in the coordination. The nitroso oxygen atoms possess short intramolecular contacts with thiazole sulphur atoms, with d(S--- O) at 2.605(3) (1) and 2.676(3) A (2), which may be attributed to a strong intraligand interaction.
Hydrothermal Synthesis and Crystal Structure of the New Manganese(II) Thioantimonate(III), Mn(en)3Sb4S7
Authors: Bensch Wolfgang , Schur Michael
Published: February 2015

The reaction of manganese with antimony and sulfur in an aqueous ethylenediamine (en) solution under hydrothermal conditions gives Mn(en)3Sb4S7. The structure of the title compound consists of Mn(en)3
2+ cations and infinite one-dimensional (Sb4S7
2-)„ anions forming slabs via long secondary interchain Sb···S bonds. A comparison between phases with polymeric (Sb4S7
2- )„ anions shows in general a trend towards a lower dimensionality of the thioantimonate assembly with increasing cation size. In the title compound the lowest number of interchain Sb···S interactions is observed among other phases with chainlike Sb4S7
2- anions.
Bondenolide, a New Diterpenoid from the Seeds of Caesalpinia bonduc
Authors: Ahmad Viqar Uddin , Ali Mumammad Shaiq , Usmanghani K.
Published: February 2015

A new diterpenoid named as bondenolide (1) was isolated from the ethyl acetate soluble part of the methanolic extract of Caesalpinia bonduc (seeds). In addition to 1, four known triterpenoids: α-amyrin [12-ursen-3β-ol], β-amyrin [12-oleanen-3β-ol], lup-20(29)-en-3β-ol, lup-20(29)-en-3β-yl acetate and two known sterols: β-sitosterol [24(R)-stigmast-5-en-3β-ol] and β-sitosteryl galactoside [3-O-β-D -galactopyranosyl-stigmasta-5-enen] were also isolated from the same source.
Enzymatic Racemic Resolution of a Fluorinated Substrate and Syntheses of E and Z Alkenes as Precursors for Some Biologically Active Fluorohexoses
Authors: Ali Muhammad Shaiq , Kitazume Tomoya , Ahmad Viqar Uddin
Published: February 2015

A fluorinated substrate 6 was prepared and then the enantiomers (6a and 7a) were separated by an enzyme in presence of an acetylating agent. The optical purity of 6a and 7a were determined by derivatising them into their MTPA -esters and then by taking their 19F NMR spectra. It was observed that, PL 266 (enzyme), benzene (solvent), 24 h (time), 40 °C (temp.) and vinyl acetate (acetylating agent) were the ideal conditions for racemic resolution. The optical purity was further improved by changing the solvent (hexane), amount of enzyme (PL 266; 3000 units), reaction time (12 h) and amount of acetylating agent (vinyl acetate; two molar). The optically pure species was used for the preparation of E and Z alkenes.
Notizen: Synthesis of N,C,C-Trilithio-2,5-diallyl-pyrrole and its Solvent-Controlled Reactions with Electrophiles Notizen
Authors: Wrackmeyer Bernd , Ordung Iris , Schwarze Bernd
Published: February 2015

2,5-Diallylpyrrole 1 reacts with an excess of nBuLi in hexane/diethylether to give the N,C,Ctrilithio reagent 2. 7Li NMR spectra of 2 in THF/ HMPTA at low temperature indicate the presence of an ionic species. Reactions of 2 in THF with electrophiles such as H2O, D2O, MeI, Me3SiCl and Me3SnCl lead selectively to the cisisomers 3a - 6a, whereas the analogous reactions in hexane or diethylether afford mixtures containing both cis- and rram-isomers (e.g. 3b).
Die Kristallstrukturen von PHF4, PH2F3 und PHF2. Moden molekularer Packung bei tiefer Temperatur [1] / The Crystal Structures of PHF4, PH2F3 and PHF2. Molecular Packing Modes at Low Temperature
Authors: Klapdor Martin Frank , Beckers Helmut , Poll Wolfgang , Mootz Dietrich
Published: February 2015

The title com pounds have been prepared in partly new ways and their crystal structures determined. The molecular geometries are found similar to those of the respective gas phases and those obtained by ab initio calculations. On the intermolecular level, there are indications of weak hydrogen bonds P-H···F in all three structures and of likewise weak fluorine bridges P-F···P in PH2F3 and PHF2 with the latter further featuring a close P···P contact.
Imidazolin-2-iminato-Derivate der Thiokohlensäure [1] / Imidazolin-2-iminato Derivatives of Thiourea [1]
Authors: Kuhn Norbert , Fawzi Riad , Maichle-Mößmer Cacilia , Steimann Manfred , Wiethoff Jörg
Published: February 2015

From 2-trimethylsilylimino-1,3-dimethylimidazoline (6, ImN-SiMe3) and CSCl2 the imidochlorothionic acid [ImN=C(S)Cl (7) is obtained; 7 gives with AlCl3 the cationic isothiocyanate [ImN=C=S]AlCl4 (9). The corresponding imidothiourea ImN=C(S)NEt2 (12) is formed reacting Et2NC(S)Cl (10) and ImNLi (11). The reaction of ImN=C(S)SSiMe3 (13) with iodine gives the dicationic species [{ImN=C(SSiMe3)S}2](I3)2 (14) which is transformed into the protonated imidothiourea [ImN=C(S)N(H)Im]I (16) by polar solvents. From 16 the imidothiourea (ImN)2CS (8) is obtained as a polymeric solid. The strong π-electron donor ability of the imido substituent ImN is revealed by the X-ray structure analyses of 12 and 16.
On the Mechanism of Cleavage of Thioacetals Promoted by Copper(II) Sulphate Adsorbed on Silica Gel
Authors: Caballero Gerardo M. , Gros Eduardo G.
Published: February 2015

A probable mechanism of the cleavage reaction of thioacetals by copper(II) sulphate adsorbed on silica gel involves: formation of a chelate between sulphur atoms and copper(II), previously coordinated with hydroxyl groups on the silica surface, and the subsequent hydrolysis promoted by hydroxyl groups on the silica gel surface.
Untersuchungen zum quasibinären System Bi2Te3/BiCl3/Investigations on the Pseudobinary System Bi2Te3/BiCl3
Authors: Petasch U. , Hennig C. , Oppermann H.
Published: February 2015

The phase diagram of the pseudobinary sytem Bi2Te3/BiCl3 was investigated by DTA, total pressure measurements, and X-ray phase analysis. Only BiTeCl exists as a ternary phase in this system. The compound melts incongruently at 430 °C. The heat of formation and the standard entropy of BiTeCl were calculated from vapor pressure data:

ΔH°B (BiTeCl, f, 298) = (-39,5 ± 1,6) kcal/mol; S° (BiTeCl, f, 298) = (34,4 ± 2,7) cal/K· mol.

The heat of formation of BiCl3 was determined on the basis of the heat of solution of BiCl3 and Bi2O3, and the heat of formation of Bi2O3: ΔH°B (BiCl3, f, 298) = (-95,9 ± 0,9) kcal/mol.
Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalyse von cis- und trans-[ReCl4 (NCSe)(SeCN)]2- / Crystal Structures, Vibrational Spectra, and Normal Coordinate Analysis of cis- and trans-[ReCl4 (NCSe)(SeCN)]2-
Authors: Strueß S. , Preetz W.
Published: February 2015

The crystal structures of cis-(n-Bu4N)2[ReCl4(NCSe)(SeCN)] (monoclinic, space group P21/n a = 10.794(3), b = 11.687(3), c = 35.716(4) Å, β = 96.97(1)°, Z = 4) and trans- (CH2Py2)[ReCl4(NCSe)(SeCN)] (monoclinic, space group P21/c, a = 8.348(2), b = 7.518(1), c - 31.295(7) Å, ß = 97.12(2)°, Z = 4) have been determined by single crystal X-ray diffraction analysis. Based on the molecular parameters of the X-ray determinations the low temperature (10 K) IR and Raman spectra of the (n-Bu4N) salts have been assigned by normal coordinate analysis. The valence force constants are fd(ReN) = 1.68 and fd(ReSe) =1.15 mdyn/Å.
Synthese und Kristallstruktur von [Au(AuNCO)(AuPPh3)8]Cl / Synthesis and Crystal Structure of [Au(AuNCO)(AuPPh3)8]Cl
Authors: Pethe Joachim , Strähle Joachim
Published: February 2015

The photolysis of Cr(CO)6 and Ph3PAuN3 (1:2) in thf yields the unstable cluster cation [(Ph3PAu)5Cr(CO)4]+ that slowly decomposes to form the new homometallic gold cluster [Au(AuNCO)(AuPPh3)8]Cl. The cluster compound crystallizes in form of red needles in the tetragonal space group I4 with a = 2214.1(3), c = 1408.9(2) pm, and Z = 2. The inner skeleton of the cluster with the symmetry C4 consists of a centered square antiprism of nine Au atoms with the square faces of the antiprism being bridged by the AuNCO group, and a Cl- anion, respectively. The shortest Au-Au distances exist between the central and the 8+1 peripheral Au atoms ranging between 263.5( 1) and 270.6(3) pm, the four Au-Cl distances are 280(1) pm.
Dimers [Al2N6]12- and Chains 1
∞[AlN4/2
3-] in the Crystal Structures of Ca6[Al2N6] and Ba3[Al2N4]
Authors: Ludwig M. , Niewa R. , Kniep R.
Published: February 2015

Pale yellow transparent single crystals of Ca6[Al2N6] (P21/c, No. 14, a = 693.7(3), b = 614.9(3), c = 987.1(5) pm, ß = 94.01(5)°; Z = 4) and colourless transparent single crystals of Ba3[Al2N4] (Pnna, No. 52, a = 617.9(2), b = 1005.2(4), c = 1023.0(4) pm; Z = 4) were obtained from reactions of mixtures of the representative metals with nitrogen at Tmax = 1000 °C. The crystal structure of Ca6[Al2N6] contains isolated units [Al2N6]12- built of two edge-sharing tetrahedra. Ba3[Al2N4] is an isotype of Sr3[Al2N4]. The crystal structure contains infinite chains 1
∞ [AlN4/2
3-] of trans edge-sharing tetrahedra.
Zur Kristallchemie des ersten Blei-Zink-Silicium-Telluroxids: PbZn4SiTeO10 / On the Crystal Chemistry of the First Lead Zinc Silicon Tellurium Oxyde PbZn4SiTeO10
Authors: Wedel B. , Sugiyama K. , Hiraga K. , Itagaki K.
Published: February 2015

Single crystals of the new lead zinc silicon tellurium oxide PbZn4SiTeO10 have been prepared by solid state reaction in air. The compound is colourless and crystallizes in orthorhombic symmetry, space group D16
2h Pnma, with the cell parameters: a = 6.542 (5), b = 15.624(4), c = 8.280(4) Å, Z = 4. The structure has been determined from a single crystal X-ray study and refined to the conventional values R = 0.032 and wR(F2) = 0.050. Zn2+ and Si4+ show tetrahedral and Te6+ octahedral coordination by O2-.The crystal structure is dominated by a 3
∞ [Zn4O10]12- framework with isolated TeO6
6+ and SiO4
4+ polyhedra. Pb2+ ions are incorporated in the network. The centres of negative charge of the lone pairs of Pb2+ are estimated by calculations of the Coulomb term of the lattice energy