bluuebunny/crossref_metadata_2025 huggingface dataset:
Verteilung und Valenz der Kationen in Spinellsystemen mit Eisen und Vanadium, VII Die Nichtstöchiometrie des Spinells FeV2O4 / Distribution and Valence of the Cations in Spinel Systems with Iron and Vanadium, VII The Nonstoichiometric Spinel FeV2O4
Authors: Riedel Erwin , Kähler Jörg
Published: March 2015

FeV2O4 has been prepared under oxygen with pressures between 10-16.4 and 10-9.9 bar. X-ray and Mössbauer investigations show that FeV2O4 is not stoichiometric but contains Fe(III), and that an additional phase of corund type has been formed. At 1000 °C and pO2, = 10-16.2 bar the spinel with the lowest Fe(III) content, Fe2+(Fe0.03
3+V1.97
3+)O4, has been prepared.
Hexacyanomanganate(III) mit Kryolithstruktur: Cs2NaMn(CN)6 und Cs2KMn(CN)6 / Hexacyanomanganates(III) with Cryolite Type Structure: Cs2NaMn(CN)6 and Cs2KMn(CN)6
Authors: Ziegler Bernd , Haegele Robert , Babel Dietrich
Published: March 2015

The crystal structures of the isotypic monoclinic cyano complexes Cs2NaMn(CN)6 (a = 759.7(1), b = 780.6(1), c = 1095.0(1) pm, β = 90.07(1)°) and Cs2KMn(CN)6 (a = 769.8(2), b = 820.4(1), c = 1120.7(2) pm, β = 90.25(1)°) have been refined from single crystal X-ray data in space group P21/n, Z = 2 (wR = 0.039 and 0.027, resp., using 1639 and 1732 independent reflections). The compounds are isostructural with cryolite, Na3AlF6, showing quite similar position parameters and nearly regular octahedra (average Mn—C= 198.8/199.6pm, C—N = 114.7/114.4pm for Na/K compound, resp.). The tilting of octahedra [Mn(CN)6]3—, [NaN6] (Na—N = 248.5 pm) and [KN6] (K—N = 280.0 pm) is compared to that of other cyano-cryolites and rationalized using radius ratio arguments in the form of a tolerance factor relation.
Bildung und Struktur von Bis(2,6-dimethoxyphenyl)nitramin, [2,6-(MeO)2C6H3]2NNO2 / Formation and Structure of Bis(2,6-dimethoxyphenyl)nitramine, [2,6-(MeO)2C6H3]2NNO2
Authors: Heuer Lutz , Schmutzler Reinhard , Schomburg Dietmar
Published: March 2015

Bis(2,6-dimethoxyphenyl)nitramine (1) was found to be one of the products of the reaction of nitryl chloride, NO2Cl with 2,6-dimethoxyphenyl lithium. 1 was characterized through its NO2 vibrations in the IR spectrum, vas = 1540 cm-1 and vs = 1290 cm-1, and its identity was confirmed by its elemental analysis, 1H and 13C NMR data, and its mass spectrum. According to a single crystal X-ray structure determination, 1 is nearly planar about the central Ν—Ν bond; the Ν—Ν bond length is 136.3 pm. In addition, two further products of the reaction were also characterized, 1-chloro-2,6-dimethoxybenzene (2) and 2,4-dichloro-1,5-dimethoxybenzene (3).
Bor-stabilisierte Ν,Ο-Carbene, II Röntgenstrukturanalyse von (trans-4,5-Dimethyloxazolidin-2-yliden)triphenylbor und N-Alkyliengen / Boron Stabilized Ν,Ο-Carbenes, II X-Ray Structure of (trans-4,5-Dimethyloxazolidin-2-ylidene)triphenylboron and N-Alkylations
Authors: Fehlhammer Wolf Peter , Hoffmeister Hans , Boyadjiev Borislav , Kolrep Thomas
Published: March 2015

The X-ray structure analysis of (trans-4,5-dimethyloxazolidin-2-ylidene)triphenylboron reveals a stereochemistry of the carbene ligand which is almost identical with that in transition metal complexes. Deprotonation of triphenylboron stabilized oxazolidin-2-ylidenes with NaH leads to (oxazolin-2-ato)borates, which have been N-alkylated with [R3O+][BF4~] or RI under mild conditions.
Studies on Condensed Pyrazoles. A New Route for Synthesis of Pyrazolo[4,3-c]pyrazoles
Authors: Elnagdi Mohamed Hilmy , Elghandour Ahmed Hafez Hussien , Sadek Kamal Usef , Ramiz Mahmoud Mohamed Mahfouz
Published: March 2015

A novel synthesis of pyrazolo[4,3-c]pyrazoles via 1,5-dipolar cyclization of products of coupling of 2,3-dimethyl-1-phenyl-5-oxo-3-pyrazolin-4-diazonium chloride with active methylene reagents is reported.
Zur Stereochemie von Pterocarpanoiden — eine theoretische Studie / On the Stereochemistry of Pterocarpanoids — a Theoretical Study
Authors: Schöning Axel , Friedrichsen Willy
Published: March 2015

Calculations (AM 1, molecular mechanics) on pterocarpanoids and related compounds (homo-, heteroanalogues) are reported.
Synthesis and Activity of Juvenile Hormone Analogues (JHA), Part II
Authors: Rodriguez Juan B. , Gros Eduardo G. , Stoka Angel M.
Published: March 2015

Several derivatives of 4-phenoxyphenoxy-ethyl and 4-phenoxyphenylethyl bearing carbonate and thiolcarbonate as functional groups were synthesized. The products were tested for their respective juvenile hormone activity for Triatoma infestans. None of them showed an activity comparable to that of Fenoxycarb which was used as the standard control. The synthetic procedures and the biological results are discussed.
Die Kristallstruktur von Na3Ga8Sn3 und die Interpretation der Bindungsverhältnisse auf der Basis der Wadeschen Regeln und des Zintlkonzeptes / The Crystal Structure of Na3Ga8Sn3 and the Interpretation of its Chemical Bonding According to Wade’s Rules and the Zintl Concept
Authors: Blase Wolfgang , Cordier Gerhard
Published: March 2015

The crystal structure of Na3Ga8Sn3 (a = 1532.7(7), b = 890.7(6), c = 1224.9(8) pm; β = 129.6(2)°, space group C2/m) contains Ga12 icosahedra and puckered layers of condensed sixmembered Ga/Sn rings, which are interconnected by additional Ga/Sn atoms to a three-dimen-sional framework. The Na content of the compound correlates with the number of electrons necessary for a stable electron configuration in the anionic partial structure.
Neue Verbindungen Ag2HgMX4 mit Wurtzstannitstruktur / New Compounds Ag2HgMX4 with the Wurtzstannite Type Structure
Authors: Haeuseler H. , Himmrich M.
Published: March 2015

Three new compounds, Ag2HgGeS4, Ag2HgSnS4, and Ag2HgSnSe4, crystallizing in the wurtzstannite type structure have been prepared by solid state reactions at 700°C and characterized by X-ray powder methods. A fourth compound of similar composition Ag2HgGeSe4, with an hitherto unknown structure crystallizes cubically with a = 10.796 A.
127I, 185Re and 187Re Solid State NMR Measurements on (CH3)4AsIO4 and (CH3)4AsReO4
Authors: Grommelt M. , Burkert P. K.
Published: March 2015

Tetramethylarsonium-metaperiodate shows 127I solid state NMR signals without any visible quadrupole splitting. Due to the very large nuclear quadrupole moments of the rhenium isotopes 185,187Re, the analogous Re compound exhibits the expected second order quadrupole NMR effects. The measured 185,187ReRe NMR powder spectra contain superimposed signals arising from two different types of ReO-
4 tetrahedra, indicating that part of the ReO4
- anions deviate only slightly from tetrahedral symmetry, while the other part are nearly undistorted ReO4
- anions.

The temperature dependence of the solid state NMR spectra reveals phase transitions for both compounds, which are confirmed also by DSC analyses. Furtherm ore, the DSC analysis of the Re compound again proves the existence of the two different types of ReO4
- tetrahedra in the lattice of the high temperature modification.
Cyclische Diazastannylene, XXX [1] Symmetrisch und asymmetrisch substituierte German- und Stannandiyle mit Amid-, Alkoholat- und Thiolat-Liganden, Teil I [2] / Cyclic Diazastannylenes, XXX [1] Symmetrically and Asymmetrically Substituted Germane- and Stannanediyls with Amide, Alcoholate and Thiolate Ligands, Part I [2]
Authors: Veith M. , Hobein P. , Rösler R.
Published: March 2015

Chelates of Ge(II) and Sn(II)

Symmetrically and unsymmetrically substituted germane- and stannanediyls as well as chelated bis(amino)- or aminooxogermanium- and -tinmonohalides have been obtained from cyclic bis(amino)germane- and stannanediyls by treatment with tert-butylamine, tert-butanol and tert-butylmercaptane. The following compounds have been synthesized: GeX2 (X = OtBu (5), StBu (6)), Sn(StBu), (9), GeXCl (X = N(H)tBu (21), OtBu (22)), SnXCl (X = N(H)tBu (23), OtBu (24), StBu (25), OMe (28)) and Sn(OtBu)Br (27). In the series of the chelates Me2Si(NtBu)(NHtBu)GeCl (13), Me2Si(NtBu)(OtBu)SnX (X = Cl (18), OMe (19)) and the bischelate [Me2Si(NtBu)(OtBu)]2Sn (20) have been prepared. When 18 is allowed to react with aluminiumtrimethyl Me2Si(NtBu)(OtBu)AlClMe is formed, a compound with a center of chirality at the aluminium atom. X-ray structure determinations have been performed on single crystals of 6, 8, 9, 13, 22 and 24. 6, 8, 22 and 24 form molecular dimers with c.n. of 3 at the Ge or Sn atoms, resp. While the tBu-S ligands are syn with respect to the central Ge2S2 ring in 6 (symmetry approaching C2v), the tBu-O ligands are anti to the central Sn2O2 ring in 8 (symmetry Ci). 9 forms a coordination polymer with all Sn atoms in a Ψ-trigonal-bipyramidal and all S atoms in a Ψ-tetrahedral environment. The germanium atom in 13 is coordinated by a chlorine, a λ3- and a λ4-nitrogen atom, the two nitrogen atoms being connected by as dimethylsilyl group. The hydrogen and chlorine atom of 13 are found at the same side of the four-membered chelate ring. The two unsymmetrically substituted, homologous compounds Ge(O/tBu)Cl (22) and Sn(OtBu)Cl (24) are found to form dimers via O→Ge resp. O→Sn bonds. While the chlorine atoms in 22 are syn with respect to the four-membered ring, they are anti in the case of molecule 24.
Amphiphilic Carbohydrate-Based Mesogens, 4 [1]. Synthesis of a Homologous Series of Mesogenic 1-O-n-Alkyl-D-mannitols
Authors: Dahlhoff Wilhelm Volker
Published: March 2015

Regioselective reduction of a homologous series of O-n-hexyl to O-n-hexadecyl 2,3:5,6-bis-O-ethylboranediyl-β-D-mannofuranosides, la-k is achieved with ethyldiboranes(6) in the presence of 9-methanesulfonyloxy-9-borabicyclo[3.3.1] nonane [MSBBN]. After deboronation the mesogenic 1-O-n-alkyl-D-mannitols 2a-k are obtained, the liquid crystal ranges and solid state transitions of which are determined by D.S.C.
[Na-15-Krone-5]2[ZrF2Cl4] und (PPh4)2[ZrCl6] · 2 CH2Cl2; Synthesen, IR-Spektren und Kristallstrukturen / [Na-15-Crown-5]2[ZrF2Cl4] and (PPh4)2[ZrCl6] · 2 CH2Cl2; Syntheses, IR Spectra, and Crystal Structures
Authors: Hartmann Eva , Dehnicke Kurt , Fenske Dieter , Goesmann Helmut , Baum Gerhard
Published: March 2015

[Na-15-crown-5]2[ZrF2Cl4] has been prepared by the reaction of the amidinato complex [Ph—C(NSiMe3)2ZrCl3]2 with sodium fluoride in acetonitrile suspension, as well as by the reaction of ZrCl4 in acetonitrile, both in the presence of 15-crown-5. On an analogous route (PPh4)2[ZrCl6] · 2 CH2Cl2 has been prepared by the reaction of [Ph—C(NSiMe3)2ZrCl3]2 with PPh4Cl in CH2Cl2 solution, as well as by the reaction of ZrCl4 with PPh4Cl in CH2Cl2. The compounds are characterized by their IR spectra and by crystal structure determinations.

[Na-15-crown-5]2[ZrF2Cl4]: Space group Ρ21/a, Z = 4, 6589 observed independent reflexions, R = 0.069. Lattice dimensions at 20°C: a = 1705.0(9), b = 1092.4(6), c = 1906.5(10) pm, β = 113.14(3)°. [Na-15-crown-5]2[ZrF2Cl4] forms ion triples, in which both sodium ions are sevencoordinate by five oxygen atoms of the crown ether molecules, as well as by a fluorine and a chlorine atom of the cis-[ZrF2Cl4]2- unit.

(PPh4)2[ZrCl6] · 2 CH2Cl2: Space group P1̄, Z = 1, 4831 observed independent reflexions, R = 0.041. Lattice dimensions at 20°C: a = 1030.1(5), b = 1124.8(6), c = 1245.6(6) pm, α = 70.81(3), β = 80.61(4), γ = 80.39(4)°. The compound has an ionic structure with ZrCl6
2- ions of symmetry Ci.
Die Kristallstrukturen von Verbindungen des Typs A2TeX6 (A = K, NH4, Rb, Cs; X = Cl, Br, I) / The Crystal Structures of Compounds A2TeX6 (A = K, NH4, Rb, Cs; X = Cl, Br, I)
Authors: Abriel Walter , du Bois André
Published: March 2015

With the determination of the crystal structure of (NH4)2TeI6 the list of the descriptions of A2TeX6 structures is further completed. At 293 K three structure types are observed with an antifluorite packing of cations and anions: The cubic K2PtCl6 type structure (space group Fm 3̄ m, Z = 4), the tetragonal Rb2TeI6 type structure (space group P4/mnc, Z = 2), and the monoclinic K2TeBr6 type structure (space group P21/n, Z = 2). The latter type was found for (NH4)2TeI6 with a = 8.0694(7), b = 8.0926(9), c = 11.7498(8) Å and β = 89.605(8)° and refined to a final Rw of 0.065. From ionic radii ratios the symmetry of the A2MX6 type structures can be predicted including a prediction of low temperature instability (soft mode condensation). Group-subgroup relationships connect the corresponding space groups and the space groups of the high/low temperature polymorphs.
Elektrochemische Untersuchungen von BEDT-TTF / Electrochemical Investigations of BEDT-TTF
Authors: Müller Harald , Fritz Heinz P. , Lerf Anton , Besenhard Jürgen O.
Published: March 2015

The electrochemistry of BEDT-TTF+ was investigated by means of cyclic voltammetry in solvents most frequently used for the electrocrystallization of radical cations of this donor. It can be shown that the reversibility of redox reactions is decreasing with the scan rate, with a significant influence of solvent. The results presented allow conclusions about the mechanism of electrocrystallization.
Das System Pyridin-Chlorwasserstoff: Bildung und Struktur kristalliner Addukte / The System Pyridine-Hydrogen Chloride: Formation and Structure of Crystalline Adducts
Authors: Mootz Dietrich , Hocken Jörg
Published: March 2015

The melting diagram of the system pyridine-hydrogen chloride was determined by DTA. It reveals the existence of intermediary solid complexes pyridine · xHCl with x = 0.5, 1, 2, 4 and 6. The structures of those with x = 1 (room-temperature phase), 2, 4 and 6 were determined from single-crystal MoKa diffractometer data at low temperatures. Pyridinium and chloride ions and, with the exception of the mono-adduct, hydrogen chloride molecules are hydrogen-bonded into various discrete molecular and complex-ionic structural units. Among these are the first poly-(hydrogen chloride) anions, HnCln+1
- or [Cl(HCl)n]- with n > 1 (viz. n = 2, 4 and 5), characterized by crystal structure analysis.
Relationship between the Electronic Structure and Acidic-Basic Properties of 4-Substituted Pyridine N-Oxides
Authors: Chmurzyński Lech , Liwo Adam , Tempczyk Anna
Published: March 2015

CNDO/2 and MNDO calculations on pyridine N-oxide (PyO), 4-nitro- (4 NO2PyO), 4-methyl-(4 PicO), 4-methoxy- (4 MeOPyO), and 4-N′,N′ -dimethylamine-pyridine N-oxide (4 N′,N′Me2PyO) and on their protonated forms have been carried out. Unknown geometries have been obtained by optimization of the MNDO energy. It has been shown that for 4 NO2PyO, 4 MeOPyO, and 4 N′,N′Me2PyO N-oxide oxygen protonated forms are much more energetically stable than the forms protonated on substituents. The calculated ionization potentials and dipole moments of the compounds studied are in good agreement with the experimental data. Both CNDO/2 and MNDO protonation energies correlate well with the experimental pKa values determined in four different solvents: acetonitrile, propylene carbonate, nitromethane, and water, the slopes being however much less than unity which indicates the important role of the solvation effect. Based on the parameters of the correlations obtained the protolytic and solvation properties of the solvents studied have been discussed.
Synthesis of Water Soluble Undecagold Clusters for Specific Labelling of Proteins
Authors: Jahn Werner
Published: March 2015

A highly water soluble undecagold cluster was prepared using a N-hydroxyethyl-N-acetyl-derivative of 4,4′,4″-phosphinidynetri(benzenemethanamine). Monofunctional clusters were synthesized in high yield by the exchange of ligands with phosphines having one free amino group. The clusters can be used for heavy atom labelling of proteins after introduction of a reactive maleimido group.
Notizen: Die Kristallstruktur von [LFe]Br3 · 4 H2O — ein low-spin-Hexamineisen(III)-Komplex (L = 1,2-Bis(1,4,7-triaza-1-cyclononyl)ethan) / The Crystal Structure of [LFe]Br3 · 4 H2O — a Low Spin Hexamineiron(III) Complex (L = 1,2-Bis(1,4,7-triaza-1-cyclononyl)ethane)
Authors: Geilenkirchen Arnd , Wieghardt Karl , Nuber Bernhard , Weiss Johannes
Published: March 2015

The unit cell of [LFe]Br3 · 4 H2O (L = 1,2-bis-(1,4,7-triaza-1-cyclononyl)ethane) is monoclinic, space group P21/c, with a = 9.609(3), b = 17.75(1), c = 14.537(6) Å, β = 104.12(3)°, and Z = 4. The iron center is in a distorted trigonal prismatic environment of six nitrogen atoms.
Darstellung von SCl2F+MF6~ (M = As, Sb) und zusammenfassende Betrachtung der Kationen SClnF3-n
+ (n = 0-3) [1] / Preparation of SCl2F+MF6~ (M = As, Sb) and a Comprehensive Discussion of the Cations SClnF3-n
+ (n = 0-3) [1]
Authors: Minkwitz Rolf , Nowicki Gabriele
Published: March 2015

The preparations and characterizations of compounds SCl2F+MF6~ (M = As, Sb) are reported. They are yellowish hydrolysable solids, with a strong tendency towards symmetrization in solution. The mass spectra data indicate the formation of SCl2F2 on thermolysis. The series of SClnF3-n
+-cations (n = 0—3) is now complete, and a comprehensive discussion of the spectroscopic data is given.
Synthese und Struktur von (MeSe)3Sb / Synthesis and Structure of (MeSe)3Sb
Authors: Breunig Hans Joachim , Güleç Sabahittin , Krebs Bernt , Dartmann Mechtild
Published: March 2015

Tris(methylseleno)stibane (1) has been prepared by reaction of Sb with Me2Se2. The crystal structure of 1 consists of (MeSe)3Sb molecules with trigonal pyramidal SbSe3 units (average distances Sb—Se 2.580 Å and Se—C 1.97 A, angles SeSbSe 83-102°). Intermolecular Sb···Se contacts of 3.55-3.66 Å lead to a distorted octahedral coordination at Sb. In the UV-VIS spectrum of the yellow solid of 1 there is a maximum of absorption at 430 nm with a slope to 540 nm. Raman emissions at 204 and 237 cm-1 are related with vs,as SbSe3.
Zum System Wasser—Fluorwasserstoff: Phasenverhalten und Kristallstruktur von 2 D2O• 3 DF, einer deuterierten Verbindung ohne protoniertes Analogon / Concerning the System Water—Hydrogen Fluoride: Phase Behaviour and Crystal Structure of 2 D2O· 3 DF, a Deuterated Compound Lacking the Protonated Analogue
Authors: Poll Wolfgang , Lohmeyer Michaela , Mootz Dietrich
Published: March 2015

The melting diagram of the quasibinary system D2O— DF was determined by low-temperature DTA and X-ray powder diffraction. It was found to be largely similar to that of the corresponding non-deuterated system H2O—HF with the striking exception of an additional phase with a composition of its own, 2D2O· 3 DF, and stable between ca. —78 and —71°C. Its structure, determined from single-crystal MoKā diffractometer data at —150°C, is rhombohedral (space group R3c, Z = 6, a = 769.9, c = 1242.1 pm) and strongly related to that of NH, · 4 HF or NH4[F(HF)3] with also seven H (as to be compared to D) and five non-H (non-D) atoms per formula unit. But with the O atom involved in four hydrogen bonds, one O · · · O and three O · · · F. at distances of 273.9 and 259.5 pm, respectively, the compound appears to be a molecular adduct rather than an oxonium salt. The D atoms in the hydrogen bonds are distributed over two positions each. — The remaining intermediary phases of the deuterated system, i. e. D2O · DF, D2O· 2 DF and D2O · 4 DF, are isotypic to their protonated counterparts of known crystal structure. For D2O · DF and D2O-2 DF these results from powder patterns were confirmed by two more single-crystal studies. The ionic structures — D3OF and D3O[F(DF)], respectively — show no distinctive effect of the H/D substitution even on details of the interatomic geometries.
Nitridokomplexe von Molybdän(V); Synthesen, IR- und EPR-Spektren. Die Kristallstruktur von [Na(15-Krone-5)Na(THF)]2[MoNCl3 ·THF]4·2THF / Nitrido Complexes of Molybdenum(V); Syntheses, IR, and EPR Spectra. Crystal Structure of [Na(15-Crown-5)Na(THF)]2[MoNCl3·THF]4·2THF
Authors: Figge Reiner , Friebel Claus , Patt-Siebel Ute , Müller Ulrich , Dehnicke Kurt
Published: March 2015

The molybdenum nitrido complexes [Na(15-crown-5)][MoNCl3] (1), [Na(15-crown-5)]2[MoNCl4] (2), and [Na(15-crown-5)Na(THF)]2[MoNCl3·THF]4·2THF (3) have been prepared by reactions of MoNCl3 with sodium naphthalide in tetrahydrofurane (THF) in the presence of 15-crown-5. According to the EPR spectra and in agreement with the IR spectra, 1 forms dimeric ions [MoNCl3]2
2~ via chloro bridges, whereas tetrameric units [MoNCl4]4
8~ and [MoNCl3 · THF]4
4~ are present in 2 and 3, respectively. 3 was characterized by an X-ray structure determination: space group P21/c, Z = 2, 1964 observed unique reflexions, R = 0.12. Lattice dimensions at —90 °C: a = 1173(1); b = 2083(3); c = 1750(2) pm; β = 112.3(7)°. The structure consists of an ensemble of associated ions around the central [MoNCl3 ·THF]4
4~ unit. In the latter, the four Mo atoms form a square and are bridged via linear, asymmetric Mo=N—Mo groups. The (MoN)4 square is enclosed in a cube of eight Cl atoms, the Mo atoms occupying four of the cube edges. Two Na+ ions are situated in the centres of two opposing cube faces, each of the other two Na+ ions is coordinated with two Cl atoms outside of the cube; these Na+ ions are also coordinated with one THF molecule and with one 15-crown-5 molecule, respectively. The crystal also contains non-coordinated THF molecules, which exhibit strong thermal motion and/or disorder.
Darstellung und Kristallstruktur von Cs4Se16 / Preparation and Crystal Structure of Cs4Se16
Authors: Sheldrick W. S. , Braunbeck H. G.
Published: March 2015

The cesium polyselenide Cs4Se16 has been prepared by the methanolothermal reaction of Cs2CO3 and Se at 160 °C and 13 bar. [Se16]4- fragments may be regarded as containing an Se6 ring with Cs symmetry and two Se5 chains related by the crystallographic mirror plane. Se4 of the sixmembered ring, which displays a square planar geometry, participates in two relatively long Se4—Se5 bonds [2.989(4) A] to individual chains. The trans-sited Se4—Se3 bonds [2.425(4) A] are markedly longer than the remaining Se—Se bonds in the Se6 ring [2.344(4), 2.356(4) A]. Further Se—Se interactions of length 3.132(4) and 3.346(4) Å are observed between individual [Se16]4- fragments.
Salts of Phosphonic Acid Derivatives: Illustrative Examples of Solid State NMR Spectroscopy
Authors: Harris Robin K. , Merwin Lawrence H. , Hägele Gerhard
Published: March 2015

High-resolution solid state 13C, 23Na and 31P NMR data have been obtained for the acid form and for several salts of the phosphonic acids: ethane-1,2-diphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid (HEDP), and 3-amino-1-hydroxypropane-1,1-diphosphonic acid. The data provide evidence by which sample purity and crystallinity may be examined and from which the size of the asymmetric unit may be determined. In the case of the sodium salts of ethane-1,2-diphosphonic acid, the 31P and 23Na spectra provide evidence of possible motion or bond fluctionality for the phosphonic acid group.
Verteilung und Valenz der Kationen in Spinellsystemen mit Eisen und Vanadium, VIII / Distribution and Valence of the Cations in Spinel Systems with Iron and Vanadium, VIII
Authors: Riedel Erwin , Kähler Jörg , Pfeil Norbert
Published: March 2015

From lattice constants and Mössbauer data the valence distribution and an energy-level diagram of the spinel system Fe(FexV2-x)O4 have been derived. In the range 0.3 ≦ χ ≦ 1.5 the transition from normal to inverse spinels takes place. The Mößbauer spectra with 1.0 ≦ χ ≦ 2.0 consist of two sets of sextets corresponding to tetrahedral and octahedral sites. Typical values of isomer shift and internal magnetic field strength due to the different environments of the iron ion result from the superimposed sextets of the octahedral site pattern. Neighbouring V ions enhance the conduction electron density and diminish the strength of the magnetic interaction. Mößbauer data, Seebeck coefficients and activation energies lead to a model of both tetrahedral and octahedral conduction based on charge hopping. For Fe1,9V1,1 O4 there exists only one iron species.
Synthese und Reaktivität von Vinyliden-Rhodiumkomplexen mit C=CHtBu und C=CHCO2Me als Liganden [1] / Synthesis and Reactivity of Vinylidene Rhodium Complexes Containing C=CHtBu and C=CHCO2Me as Ligands [1]
Authors: Werner Helmut , Brekau Uwe
Published: March 2015

Square-planar alkyne rhodium complexes trans-[RhCl(RC=CCO2Me)(PiPr3)2] (4-6) bearing at least one electron withdrawing substituent at the C=C triple bond are prepared from [RhCl(PiPr3)2] (3) and RC=CCO2Me. Reaction of 3 with tBuC≡CH gives the isomeric alkyne (7) and alkynyl hydrido (8) rhodium complexes in a stepwise fashion. 8 can be trapped with pyridine to produce [RhH(C2tBu)Cl(PiPr3)2(NC5H5)] (10). Thermal rearrangement of 6 (R = H) and 8 leads to the formation of the vinylidene complexes trans-[RhCl(=C=CHR)(PiPr3)2] (9,12) which react with NaC5H5 in THF to give the cyclopentadienyl derivatives C5H5Rh(=C=CHR)(PiPr3) (13, 14). Reactions of 13 and 14 with sulfur afford the thioketene rhodium compounds C5H5Rh(η2-S=C=CHR)(PiPr3) which on methylation with CF3SO3CH3 in the presence of NH4PF6 give the ionic complexes [C5H5Rh(η2-SCH3=C= CHR)(PiPr3)]PF6 (18,19).
Synthese und Kristallstruktur von (S4N3)2Se2Cl10, (S4N3)2Se2Cl6 und [(S4Ν3)SeSeCl5]n / Synthesis and Crystal Structure of (S4N3)2Se2Cl10, (S4N3)2Se2Cl6, and [(S4N3)SeCl5]n
Authors: Stammler Hans Georg , Weiss Johannes
Published: March 2015

(S4N3)2Se2Cl10, (S4N3)2Se2Cl6 and [(S4N3)SeCl5]n are formed by the reaction of S4N4, Se2Cl2, and SOCl2. The structures of the three compounds where determined by X-ray diffraction. The yellow crystals of (S4N3)2Se2Cl,10 are monoclinic, space group P21/a, a = 817.5(2) pm, b = 1790.4(5) pm, c = 843.1(6) pm, β = 104.31(4)°, Z = 2. The Se2Cl,10
2- anion consists of 2 Cl-bridged distorted octahedra. (S4N3)2Se2Cl6 forms red monoclinic crystals, space group P21/c, a = 1036.5(3) pm, b = 1376.5(5) pm, c = 1400.4(4) pm, β = 100.65(2)°, Ζ = 4. In the Se2Cl6
2- anion the Se atoms have a square planar environment. The yellow crystals of (S4N3)SeCl5 are orthorhombic, space group P212121, a = 734.2(3) pm, b = 989.4(4) pm, c = 1627.4(6) pm, Z = 4. In the SeCl5
- anion the Se atom has an octahedral environment of chlorine atoms, thus forming a polymeric structure.
Metallorganische Lewis-Säuren, XLI [1] / Organometallic Lewis Acids, XLI [1]
Authors: Fritz Peter M. , Steimann Martin , Beck Wolfgang
Published: March 2015

Addition of [Re(CO)5]+ (as (OC)5ReFBF3) to compounds of the type Cp(OC)2Fe—C(S)SR (R = CH3, Fe(CO)2Cp) gives the products [Cp(OC)2Fe—C(SCH3)S—Re(CO)5]+BF4
- (1) and {Cp(OC)2Fe—C[SFe(CO)2Cp]—S—Re(CO)5}+BF4
- (2), respectively. Complex 2 has been characterized by an x-ray structure analysis. From (OC)5ReFBF3 and (Ph4P)2(OC)2Fe(η2—CS2), the complex [(Ph3P)2(OC)2Fe[μ2-η2(C,S):η1 (S′)]Re(CO)5]+BF4
- (3) has been obtained.
New Triterpene from Conyza aegyptiaca L
Authors: Metwally Mohamed Abbas
Published: March 2015

A reinvestigation of C. aegyptiaca L. gave in addition to phytol a new triterpene. Its structure was determined by IR,1H NMR and mass spectral data.
Stereoselektive Insertion von Aldehyden und Ketonen in die Metall-Kohlenstoff-Bindung eines (η6-Fulven)titan-Komplexes / Stereoselective Insertion of Aldehydes and Ketones into the Metal-Carbon Bond of a (η6-Fulvene)titanium Complex
Authors: Erker Gerhard , Korek Uwe
Published: March 2015

Thermolysis of Bis(η-methylcyclopentadienyl)diphenyltitanium (6) at 80°C yields benzene and (η6-fulvene)(η-methylcyclopentadienyl)phenyltitanium (8). Complex 8 reacts with various aldehydes and ketones by insertion into the Ti—CH2C5H4 σ-bond to stereoselectively form the metallacyclic chiral metallocene complexes [xxx] 10a—d. Difference NOE 1H NMR spectra of the acetaldehyde insertion product 10c (R1 = H, R2 = CH3) have revealed a cis-arrangement of the methyl substituent and the titanium bound σ-phenyl ligand at the central metallacyclic ring system.
Notizen: Erste Interalkalimetalltelluride: NaLiTe, KLiTe, KNaTe / First Inter Alkali Metal Tellurides: NaLiTe, KLiTe, KNaTe
Authors: Hitzbleck Rolf-D. , Vogt Petra , Sabrowsky Horst
Published: March 2015

The dark grey compounds NaLiTe, KLiTe and KNaTe have been prepared and characterized by X-ray powder diffraction. NaLiTe and KNaTe are isotypic and crystallize in the orthorhombic space group Pnma with Z = 4 formula units in the unit cell. The lattice constants are a = 774.0(1), b = 462.4(2) and c = 840.6(1) pm for NaLiTe and a = 852.1(1), b = 513.4(2) and c = 926.5(1) pm for KNaTe. KLiTe crystallizes in the tetragonal space group P4/nmm with a = 483.9(2) and c = 771.7(1) pm and Z = 2.
Notizen: Über die Interalkalimetallselenide KLiSe und KNaSe / The Inter Alkali Metal Selenides KLiSe and KNaSe
Authors: Hippler Karin , Vogt Petra , Wortmann Regina , Sabrowsky Horst
Published: March 2015

The colourless compounds KLiSe and KNaSe have been prepared and characterized by powder measurements. KLiSe crystallizes in a tetragonal lattice with a — 451.7(1), c = 7274 1(2) pm, Z. = 2 (P4/nmm). KNaSe crystallizes in the orthorhombic space group Pnma with a = 806.3(2), b = 481.7(1) and c = 865.1(2) pm, Z = 4.
Kristallstruktur von Na4OBr2 / Crystal Structure of Na4OBr2
Authors: Hippler Karin , Sitta Stephan , Vogt Petra , Sabrowsky Horst
Published: March 2015

The colourless compound Na4OBr2 has been prepared and its crystal structure determined by X-ray diffraction. Very hygroscopic Na4OBr2 crystallizes in the tetragonal space group I 4/mmm (Z = 2) with the cell parameters a = 452.1(3) and c = 1490.8(1) pm. The structure was solved from 267 symmetry independent reflections by Patterson and Fourier methods (R = 0.028; wR = 0.029). Na4OBr2 crystallizes in the anti-K2NiF4-structure type and is isotypic to Na4OI2 and K4OBr2 which have been described earlier.
Zur Reaktion von Ni8-Clustern mit Natriumamalgam. Die Kristallstrukturen von {[Ni8Hg(PPh)6(PPh3)4]·[Ni8(PPh)6(PPh3)4]} und [Ni8S6(PPh3)8] / Reaction of Ni8-Clusters with Sodium Amalgam. The Crystal Structures of {[Ni8Hg(PPh)6(PPh3)4] · [Ni8(PPh)6(PPh3)4]} and [Ni8S6(PPh3)8]
Authors: Fenske Dieter , Magull Jörg
Published: March 2015

[Ni8Cl4(μ4-PPh)6(PPh3)4] (1) reacts with sodium amalgam to form [Ni9(PPh)6(PPh3)4] (2) and {[Ni8Hg(PPh)6(PPh3)4] · [Ni8(PPh)6(PPh3)4]} (3). 3 has been characterized by X-ray crystal structure analysis. It contains two distorted cubic Ni8-clusters. All faces of the cubes are occupied by μ4-PPh ligands. At one of the cubes one nickel atom is bonded to an external mercury atom. [Ni8Cl2S6(PPh3)6] (4) reacts with sodium amalgam to form [Ni8S6(PPh3)8] (5). In this symmetrical structure all nickel atoms are bonded to three S ligands and to one PPh3.
Synthese und Kristallstrukturen von Dimethylgalliumdiphenylphosphinat und Diethylindiumdiphenylphosphinat / Synthesis and Crystal Structures of Dimethylgalliumdiphenylphosphinate and Diethylindiumdiphenylphosphinate
Authors: Hahn F. Ekkehardt , Schneider Bernd , Reier Friedrich-Wilhelm
Published: March 2015

The synthesis of diethylindiumdiphenylphosphinate and the crystal structures of dimethylgalliumdiphenylphosphinate and diethylindiumdiphenylphosphinate are reported. The two structures confirm the proposed dimeric nature of the title compounds with bridging diphenylphosphinate groups. [Ph2P(O)2Ga(CH3)]2 crystallizes triclinically, PĪ, with a = 9.483(6), b = 10.216(4), c = 8.780(9)Å, α = 101.66(5)°, β = 113.74(5)°, γ = 69.93(5)° and Ζ = 1 (dimer). [Ph2P(O)2In(C2H5)2]2 crystallizes monoclinically, C2/c, with a = 19.971(5), b = 8.590(2), c = 19.457(5)Å, β = 102.91(2)° and Ζ = 4 (dimers). Both structures contain tetrahedrally coordinated phosphorous and metal atoms.
Darstellung und Kristallstruktur zweier Polytelluride mit großen mehrfach geladenen Kationen / Determination and Crystal Structure of Two Polytellurides with Large Double and Triple Charged Cations
Authors: Klinkhammer K. W. , Böttcher P.
Published: March 2015

Two polytellurides of double and triple charged organic cations have been synthesized and their crystal structures have been determined.

K2Te3 and the iodides of 2,2,5,5-tetramethyl-2,5-diazoniahexane, [TMDH]I2, and 2,2,5,5,8,8-hexamethyl-2,5,8-triazonianonane, [HMTN]I3, respectively, are mixed together in aqueous solution in appropriate ratios. After a few hours black crystals of the polytellurides precipitate. The reaction of the double charged cation, TMDH2+, results in the tetratelluride, [TMDH]Te4, whereas that of the triple charged cation, HMTN3+, gives the tridecatelluride, [HMTN]2Te13.

[TMDH]Te4 crystallizes in the space group P21/n (a = 13.321(5) A, b = 15.940(7) A, c = 7.969(3) Å, β = 94.12(3)°). Interconnected Te4
2--polyanions are found in the structure. [HMTN]2Te13 crystallizes in the space group PĪ (a = 8.772(2) Å, b = 17.529(4) Å, c = 18.036(4) Å, a = 68.11(3)°, β = 76.73(3)°, γ = 77.08(3)°). No distinct tridecatelluride polyanions occur in the structure, but rather two crystallographically independent Te4
2--anions and one Te5
2--anion. As in [TMDH]Te4, all of the anions are interconnected.
Reaktive E=C(p – p)π-Systeme, XX [1] / Reactive E=C(p–p)π-Systems, XX [1]
Authors: Grobe Joseph , Hegemann Marianne , Le Van Duc
Published: March 2015

The vapour phase pyrolysis of the stannylphosphane Me3SnP(CF3)C2F5 (5) at 330 °C leads to 1,2-elimination of Me3SnF yielding a mixture of the two isomeric perfluorophosphaalkenes F3CP=C(F)CF3 (3) and F5C2P=CF2 (4) in a 3:1 molar ratio. 3 is more labile than 4 and proves to be similar to the perfluoro-3-phosphapent-2-ene F5C2P=C(F)CF3 (2) with respect to NMR data and chemical properties. On the other hand 4 resembles the perfluoro-2-phosphapropene F3CP=CF2 (1). These results have been deduced from the following reactivity studies: (i) The rate of dimerization being higher for 3 than for 4. (ii) Reaction of the mixture with diethylamine yielding the aminophosphane derivative F3CP(NEt2)CF(H)CF3 (13) as a product of 3 and the C-aminophosphaalkene F5C2P=C(F)NEt2 (14) as the derivative of 4. (iii) Reaction of the mixture with methanol giving the methoxyphosphane F3CP(OMe)CF(H)CF3 (15) from 3 and the secondary phosphane F5C2P(H)CF2OMe (16) from 4 as precursors. 3 and 4 prove to be effective dienophiles in reactions with 2,3-dimethyl-1,3-butadiene and 1,3-cyclohexadiene, respectively, producing the corresponding Diels-Alder adducts 9 to 12. For these preparations 5 can be used as an equivalent of 3 in a one-pot procedure at 70 °C. On the other hand the phosphane HP(CF3)C2F5 (8) is suited as precursor for 3 in preparing HX addition products.
Über die Darstellung neuer spirocyclischer N,N′-Dimethylsulfamid-substituierter Phosphorverbindungen und Ν,N′-Dimethylsulfamid-verbrückter Diphosphorverbindungen / The Preparation of New Spirocyclic N,N′-Dimethylsulphamide-Substituted Phosphorus Compounds, and of Some N,N′-Dimethylsulphamide-Bridged Diphosphorus Compounds
Authors: Jones Peter G. , Meyer Anke , Schmutzler Reinhard
Published: March 2015

The reactions of 4-chloro-1,3,5,7-tetramethyl-2,2,6,6-tetraoxa-2,6-dithia-1,3,5,7-tetraaza-4λ5-phosphaspiro[3.3]heptane (1) with trimethylsilyl compounds and sodium azide led to a series of spirocyclic N,N′-dimethylsulphamide-substituted phosphoranes (2—5). The nature of the pentaaza-spirophosphorane (4) was confirmed by an X-ray crystal structure determination (C2/c, a = 991.8(4), b = 1185.6(6), c = 1224.9(5) pm,β = 108.64(3)°, Z = 4, R = 0.041 for 1065 unique observed reflections); a crystallographic twofold axis passes through phosphorus and the nitrogen atom of the NMe2 group. The geometry at phosphorus is to a good approximation trigonal bipyramidal. The azido-spirophosphorane (5) undergoes Staudinger-type reactions with phosphorus(III) compounds (PPh3, dppm) to form the mixed-valence phosphorus compounds 6—8. The reaction of N,N′-dimethylsulphamide or N,N′-dimethyl-N,N′-bis(trimethylsilyl)-sulphamide with dichlorophosphines RPCl2 (R = Me, Ph) in a molar ratio 1:2 leads to the formation of the acyclic N,N′-dimethylsulphamide-bridged diphosphorus compounds 9 and 10, respectively. The spectroscopic properties (and, for 4, the X-ray crystal structure) of the products are compared with those of analogous urea-bridged phosphorus compounds.
tert-Butylimino-cyclopentadienyl-alkylvanadium(V)-Verbindungen Darstellung und NMR-spektroskopische Untersuchungen / tert-Butylimino-cyclopentadienyl-alkylvanadium(V) Compounds Synthesis and NMR Spectroscopic Studies
Authors: Preuss Fritz , Becker Harald , Wieland Thomas
Published: March 2015

The cyclopentadienyl compounds tC4C4H9N=VCp(NHtC4C4H9)Cl, tC4C4H9N=VCp[N(SiMe3)2]Cl, tC4C4H9N=VCp(NHtC4C4H9)(R) (R = CH3, ⁿC4H9, 5C4H9, tC4H9, CH2SiMe3), Li[(tC41H9N)2VCp(CH3)]-OEt2, tC4H9N=VCp2(NHtC4H9) and tC4H9N=VCp(CH3)2 have been prepared starting from tC4H9N = V CpCl2. All compounds obtained are characterized by 1H and 51V NMR spectroscopy; the stability of monoalkylvanadium(V) complexes is discussed.
Einkristallzüchtung und Röntgenstrukturanalyse des polymeren 1:1-Komplexes zwischen CuCl2 und Pyridazin / Crystal Growth in Gels and X-Ray Characterization of the Polymeric 1:1-Complex of CuCl2 with Pyridazine
Authors: Fetzer Th. , Lentz A. , Debaerdemaeker T. , Abou-El-Wafa O.
Published: March 2015

Single crystals of Cu(pdz)Cl2 were grown by using gel methods with tetramethoxysilane as the gel-forming reagent. Thermal decomposition is interpreted. Crystal data for the complex : monoclinic, space group C2/c with a = 938.3(3) pm, b = 1242.9(3) pm, c = 675.7(4) pm, β = 128.48(5)°. A crystal structure analysis reveals CuCl2 molecules connected by pyridazine in the form of zigzag-chains. Between these chains there are only Van-der-Waals-Interactions.
Synthese primärer und sekundärer Phosphane durch selektive Alkylierung von PH3 unter Phasentransferbedingungen / Synthesis of Primary and Secondary Phosphines by Selective Alkylation of PH3 under Phase Transfer Conditions
Authors: Langhans Klaus P. , Stelzer Othmar , Svara Jürgen , Weferling Norbert
Published: March 2015

Primary phosphines, RPH2, may be synthesized selectively by alkylation of phosphine, PH3, with alkyl halides RX (R = Me, Et, n-Bu, 2-Bu, C16H33, CH2=CH–CH2, Ph–CH2, 2-Py–CH2–CH2; X = Cl, Br) and concentrated aqueous KOH as auxilliary base in dimethylsulfoxide as a solvent or in two phase systems employing phase transfer catalysts. Under more rigorous conditions secondary phosphines R2PH (R = Me, n-Bu, CH2=CH–CH2) are also accessible in good yields. Using 1,3-dibromo(chloro)-propane or -butane diprimary phosphines H2P–(CH2)2–CHR–PH2 (R = H, Me) are obtained, while 1,4-dibromopentane in a high yield cyclization reaction leads to 2-methylphospholane (12) with a chiral C-atom in a-position.
Cp′—X—Cp′-überbrückte μ-Cyclooctatetraen- und -trien-Zweikernkomplexe des Chroms sowie Vanadiums (Cp′ = η5-C5H4, X = CH2, SiMe2, GeMe2) / Binuclear Cp′–X–Cp′-Bridged μ-Cyclooctatetraene and -triene Complexes of Chromium as well as Vanadium (Cp′ = η5-C5H4, X = CH2, SiMe2, GeMe2)
Authors: Bachmann Bernd , Baum Gerhard , Heck Jürgen , Massa Werner , Ziegler Bernd
Published: March 2015

Synfacial binuclear μ-Cot complexes of the general formula X(Cp′M)2— μ-Cot with Cp′—X—Cp′ as an additional bridging group (M = V, Cr; Cot = cyclooctatetraene) can be prepared by a one-pot reaction of the appropriate metal dichlorides with K2Cot and Li2[(C5H4)2X]. For M = V the vanadocenophanes {V(Cp'2X)}2 (X = SiMe2, GeMe2) are isolated as by-products. Depending on the conditions of work-up for M = Cr µ-(σ:η3:η2-cyclooctatriene) complexes can be obtained instead of the μ-Cot compounds. X-ray structure determinations of several μ-Cot species attest only a poor influence of the bridging group X on the metal metal bond. Low temperature 1H NMR spectra of the dichromium μ-Cot complexes show that the rapid Cotrotation can be frozen below T = 200 K. Temperature dependent 1H NMR studies indicate a diamagnetic-paramagnetic equilibrium for the binuclear μ-C8H10 compounds, wherein a Cr,Crmultiple bond must be assumed.
Schwefelmonoxid als Ligand in kationischen Halbsandwich-Komplexen des Eisens und Rutheniums [1] / Sulfur Monoxide as Ligand in Cationic Halfsandwich Type Complexes of Iron and Ruthenium [1]
Authors: Schenk Wolfdieter A. , Karl Ute , Horn Michael R. , Müssig Stefan
Published: March 2015

Cationic halfsandwich type iron sulfur monoxide complexes [cpFe(L—L)(SO)]+ (L— L = dppe, cdpe) and [cp*Fe(PMe3)2(SO)]+ are obtained by transition metal-induced SO transfer from thiirane-1-oxide. With the sterically unhindered fragment [cpFe(dmpe)]+ a binuclear SO-bridged dication is formed instead. Reaction of [cpRu(PR3)2Cl] (R = Me, Ph) and [cpRu(dppe)Cl] with thiirane-1-oxide gives mixtures of the known cations [cpRuL2(SO2)]+ and [(cpRuL2)2(μ-S2)]2+, probably via the expected mononuclear SO complexes which disproportionate at low temperature. The more electron-rich cation [cp*Ru(PMe3)2(SO)]+, however, is stable. Reactions with pyridine, PMe3, and 3-chloroperbenzoic acid demonstrate that the coordinated SO can be attacked by nucleophiles as well as electrophiles.
Konformation von Anthranilsäurepeptiden, 3 [1]: Konformationen kleiner Anthranilsäure-Prolinpeptide im Kristall, in Lösung und eine semiempirische (AM 1) Beschreibung der Prolin-Ramachandran-Hyperflächen / Conformation of Anthranilic Acid Peptides, 3 [1]: Conformation of Small Anthranilic-Acid-Proline-Peptides in Crystal, in Solution and a Semi-empirical (AM 1) Description of the Proline-Ramachandran Maps
Authors: Feigel Martin , Lugert Gerhard , Manero Javier , Bremer Matthias
Published: March 2015

Starting from tert-Butyloxycarbonyl(BOC)-Anthranilic-Acid(Abz) (1), BOC-Abz-Proline-Methyl-Ester (2) is synthesized. The crystal structure of both compounds are discussed. The conformational features of the crystal structures of 2 are compared with the conformation in solution. The whole conformational area (Φ and Ψ) of the amino acid part of 2 was investigated with the semi-empirical quantummechanical method AM 1, in order to check the general availability of the influence of ester functions to depsipeptide conformations. Cyclo-anthranoyl-prolinyl (3), which had already been described in the literature, forms crystals with a high density. Two independent molecules are found in the crystal structure; these molecules have very similar conformations.
Neue Untersuchungen an Borsäureestern von Brenzcatechin und einiger Catecholamine in wäßriger Lösung und an Feststoffen / New Investigations of Boric Acid Esters of Catechole and of Some Catecholamines in Aqueous Solutions and on Solids
Authors: Mohr Siegfried , Heller Gert , Timper Ulrich , Woller Karl-Heinz
Published: March 2015

The orthoborate ion [B(OH)4]⁻ in aqueous solutions between pH 5 and 12 forms stable boric acid esters with catechole and the catecholamines DOPA, α-methyldopa, dopamine, noradrenaline, adrenaline, and adrenalone. The stoichiometries of the esters in solution, their dependence of pH value and concentration were evaluated by 11B NMR spectra and confirmed by Raman investigations in the catechole system. Additionally, Raman spectra and crystal structure investigations on solid crystalline esters confirm these results. The 1:1 esters show in the 11B NMR spectrum a chemical shift δ of around 8.1 ppm, the 2:1 esters of around 13.5 ppm. The Raman spectra of the catechole ester show lines at 744 cm-1, 826 cm-1, and 1011 cm-1 for the 1:1 ester as well as at 798 cm-1 and 840 cm-1 for the 2:1 ester. Besides the 1:1 and 2:1 ester, a 3:1 compound is found as a solid for catechole. Raman spectra of this compound, unstable in aqueous solution, showed a superposition of the 2:1 ester and free catechole. The crystal structure of the triethylammonium salt, which is monoclinic, space group Cc = Cs
4 (No. 9) with a = 925.3(3), b = 1781.1(2), and c = 1444.4(2) pm; β = 94.22(4)°; Ζ = 4; Dc = 1.229 Mg · m-3, shows that two molecules of catechole are esterified with the orthoborate ion in the form of a spiran-like four-coordinated boron atom, while the third molecule of catechole is freely inserted into the crystal. The crystal structure of adrenaloneborate-monohydrate, which is also monoclinic, space group P21/c = C2 h
5 (No. 14) with a = 942.4(4), b = 888.1(3), and c = 1337.8(3) pm; β = 96.86(5)°; Ζ = 4; Dc = 1.452 Mg-m-3, shows two condensed rings, the aromatic ring being condensed through the two phenolic O atoms with the boron atom, so building a dioxaborolane ring. The two OH-groups at the boron atom build Η-bridges with the water molecule. It may be a zwitter ion with a negative boron atom and a positive nitrogen atom.
Two New Terpenoids from Pluchea arguta Boiss.
Authors: Ahmad Viqar Uddin , Sultana Azra , Fizza Kaniz
Published: March 2015

Two new terpenoids pluchidione 1 and pluchidinol 2 were isolated from the ethyl acetate soluble portions of the whole plant of Pluchea arguta Boiss. The structures of these compounds were established by using modern spectroscopic techniques.
Notizen: Na3O(CN) — das erste Alkalimetallchalkogenidpseudohalogenid / Na3O(CN) — the First Alkali Metal Chalcogenide Pseudohalide
Authors: Hippler Karin , Sitta Stephan , Wortmann Regina , Sabrowsky Horst
Published: March 2015

The colourless compound Na3O(CN) has been prepared. The characterization by X-ray powder methods leads to a cubic primitive lattice (P m 3 m) with a = 456(2) pm (Z = 1). The structure is related to the anti-perovskite type.
Notizen: Influence of Counter Ion Structure on the Direction of the Phase Transfer Catalytic Methylation of an Enol [1]
Authors: Dehmlow Eckehard V. , Schrader Sabine
Published: March 2015

Phase transfer catalytic (PTC) methylations of deoxybenzoin by dimethyl sulfate can be steered towards enol ether formation by large, sterically shielded ammonium ions or – more strongly – by large highly delocalized phospho-iminium (and presumably other large) cations. The C-alkylation direction is favoured by small, hard ammonium ions of the type RNMe3
+ and by crown ethers, particularly benzo-crowns. O/C ratios can be varied between 0,75 and 63, the largest effects so far reported for ambident anions. These results should give guide-lines for alkylations of other ambident ions.
Darstellung und Kristallstruktur des K5Te3 / Preparation and Crystal Structure of K5Te3
Authors: Schewe I. , Böttcher P.
Published: March 2015

The structure of the first of the new alkali metal chalcogenides of the composition M5X3 has been solved (K5Te3: a = 13.742(2)Å, c = 6.364(2) Å, space group: I 4/m, Z = 4). It can be derived from the W5Si3 type of structure by substituting the · · · Si · · · Si · · · Si · · · chains by those of Te2
2--dumbbells · · · (Te–Te) · · · (Te–Te) · · · (Te–Te) · · · , both running along [001]. The Te2
2--dumbbells occur as a consequence of the necessity of charge compensation of the saltlike compound K5Te3, according to 2 K5Te3 ⇌ 10 K+ + Te2
2- + 4 Te2-. The remaining tellurium atoms not involved in the dumbbells build up strings of tetrahedra ∞
1[ΚΤe4/2], with common edges along [001]. Therefore, the resulting K–K distances in these strings of tetrahedra are extremely short (3.18 A).
Kristallstruktur und Schwingungsspektren von [(n — C4H9)4N]2[Re2F8]·2(C2H5)2O / Crystal Structure and Vibration Spectra of [(n—C4H9)4N]2[Re2F8] · 2(C2H5)2O
Authors: Henkel G. , Peters G. , Preetz W. , Skowronek J.
Published: March 2015

The dark blue title compound has been prepared by reaction of [Re,Cl8]2- and F-, both dissolved as ion pairs with [(n–C4H9)4N]+ in anhydrous CH2Cl2, and recrystallization from acetone/diethylether. Structure determination by single crystal X-ray diffractometry at 150 K reveals crystallization in the cubic system, space group Pn3̄n with a = 19.783(3)Å, V = 7742.4Å3, Z = 6. The {[Re2F8]·O(C,H5)2}2- entity consists of an axially elongated F8-cubane frame around the Re, unit, which is coordinated at one side by an ether molecule (Re–O distance 2.64(4)Å) and displaced from the center towards the ether. The Re– Re quadruple bond (2.188(3)A) is the shortest of the four octahalogenodirhenates(III). In contrast to its Cl, Br and I homologues no disorder of the Re, units is observed. The Re– F distances of 1.92(3) and 1.96(3)A are equal within the standard error, and the Re–Re–F angles are 99.9(4)⚪ and 102.6(4) , respectively. The UV-Vis spectrum of [(n–C4H9)4N]2[Re2F8] shows only the δ-δ* transition at 558 nm (ε = 771 cm2/mmol). At 10 K this band exhibits a weak vibrational fine structure with an averaged progression of 209 cm-1. The Raman spectrum is dominated by v(Re–Re) at 317.5 cm-1 with up to five overtones, the IR spectrum by v(Re–F) at 560 cm-1. Additional bands for the solvated compound at 525 and 306 cm-1 are assigned to v(Re–O) and v(Re–Re), respectively. The 19F NMR spectrum in aceton-d6 shows a singlet at –135.06 ppm; in the presence of ether an additional weak signal arises at –134.15 ppm versus external CFC13.