bluuebunny/crossref_metadata_2025 huggingface dataset:
Redoxreaktionen mit cyclopeptidartigen Chinolinderivaten als lipophil-maskierte NAD-Modellverbindungen / Redox Reactions with Cyclopeptide-Like Quinoline Derivatives as Lipophilic NAD Model Compounds
Authors: Bohnert Sabine , Gündel Wolf-H.
Published: March 2015

Quaternary salts of the amides of N-(3-quinolinecarbonyl) amino acids (7) cyclise under the influence of base to give fourteen membered rings (9). This dimerisation is a reaction with high diastereoselectivity. The addition product 9 can be regarded as lipophilic, masked NAD model compound: 9 oxidizes 2-propanol under ZnCl2 catalysis to give in high yield acetone and the 1.4-dihydroquinoline.
[1.4]Diazepino[6.5-c]chinoline mit L-Aminosäurebaustein — Darstellung und Reaktionen / [1.4]Diazepino[6.5-c]quinolines with L-Amino Acid Moiety — Preparation and Reactions
Authors: Bohnert Sabine , Gündel Wolf-H.
Published: March 2015

Quaternary salts of the amides of N-(3-quinolinecarbonyl)-N-alkyl-amino acids (6) cyclise under the influence of base to the title compounds (7). This intramolecular addition is a reaction with high diastereoselectivity, dependent on the amino acid part. 7 disproportionates to 8 and 9. 7 behaves as lipophilic NAD model compound in the reaction with 2-propanol under ZnCl2 catalysis.
Phase-Transfer Catalysed Alkylation of Enamines of some Cyclic β-Keto Carbothionic Acid Anilides with 1,2-Dibromoethane. Synthesis of Enamines of 1-Oxo-2-(3-phenyl tetrahydrothiazol-2-ylidene)-cycloalkanes
Authors: Bogdanowicz-Szwed Krystyna , Kozicka Michalina
Published: March 2015

The alkylation of morpholine enam ines of 2-oxo-cycloalkane-1-carbothionic acid anilides (1-3) with 1,2-dibromoethane under phase-transfer catalytic conditions yields enam ines of 1-oxo-2-(3-phenyl-tetrahydrothiazol-2-ylidene)-cycloalkanes (4-6). Compounds 4-6 were hydrolysed to appropriate keto derivatives 8-10. The structure of obtained com pounds was established on the basis of IR. NM R and MS spectral data.
Selektive und sensitive Bestimmung von Nicergolin und Metaboliten in biologischen Medien durch HPLC zur Erforschung seines humanpharmakologischen Verhaltens / Selective and Sensitive Quantification of Nicergoline and Metabolites in Biologie Fluids by HPLC and its Application to Pharmacokinetic Research in Human
Authors: Nieder Michael , Jaeger Halvor
Published: March 2015

A high performance liquid chromatographic method was developed to study the pharmacokinetics of nicergoline and its two main m etabolites in humans. The analytes are extracted from blood, plasma and urine into a mixture of chloroform and ether, which is optimised in terms of recovery and absence of interferences. The analytes are separated on a small bore column filled with octadecylsilica. the mobile phase was a ternary mixture of water, acetonitrile and tetrahydrofurane with diisopropylamine for pH adjustment. To maintain the chromatographic stability. the mobile phase is circulated and a saturator column inserted between pump and sampler. Nicergoline is very unstable in blood, it could not be determined in human body fluids after a single dose of 10 mg nicergoline. Metabolite 1 reaches plasma concentrations of about 2 ng/ml after 40 min. metabolite 2 gains to about 8 ng/ml after 4 h. 67% of the dosed nicergoline are excreted in urine as free metabolite 2. free metabolite 1 occurred only in trace concentrations. 18.5% of the dosed drug were excreted as conjugated metabolite 2. 1.1% as conjugated metabolite 1.
NOTIZEN. Zur Reaktion von PhSSiMe3 mit [CoCl2(PPh3)2] und (NBu4)[CoCl3(PPh3)]. Die Kristallstrukturen von (NBu4)2[Co4(SPh)6Cl4], [Co4(SPh)6Cl2(POPh3)(PPh3)] und (NBu4) [Mn2(SPh)3(CO)6] / Reaction of PhSSiMe3 with [CoCl2(PPh3)2] and (NBu4)[CoCl3(PPh3)]. The Crystal Structures of (NBu4)2[Co4(SPh)6Cl4], [Co4(SPh)6CL(POPh3)(PPh3)] and (NBu4)[Mn2(SPh)3(CO)6]
Authors: Fenske Dieter , Meyer J. , Merzweiler K.
Published: March 2015

(NBu4)2[Co4(SPh)6Cl4] (1) and [Co4(SPh)6CU(PPh3)2] (2) are prepared by the reaction of (NBu4)[CoCl3(PPh3)] and [CoCl2(PPh3)2] with PhSSiMe3 in toluene solution. The overall description of the Co4S6Cl4 core is that o f a nearly regular Co4-tetrahedron inscribed in an irregular octahedron of the bridging S atoms resulting in an “adamantane” type cage. 1 reacts with Na[Mn(CO)5] to form the dinuclear complex (NBu4)[Mn2(SPh)3(CO)6] (4). Each Mn atom is bound to three CO and three μ2-SPh ligands. The Mn-Mn contact (318.5 pm) does not indicate metal-metal bonding.
Synthese und Kristallstruktur siebengliedriger kohlenstoffhaltiger Schwefel-Stickstoffringe / Synthesis and Crystal Structure of Seven-M embered Sulfur Nitrogen Rings Containing Carbon
Authors: Roesky Herbert W. , Benmohamed Nasreddine , Keller Klaus , Keweloh Nayla , Noltemeyer Mathias , Sheldrick George M.
Published: March 2015

The reaction of ClSCF2CF2SCl and (Me3SiN)2SR2 proceeds with formation of the seven-membered ring compounds 4a, R = CH3, and 4b, R = C2H5. 4a was shown by an X-ray structure determination to contain a non-planar ring system.
Synthese und Eigenschaften von 3,6-Diorgano-3,6-dithio-1,2,4,5,3,6-tetrathiadiphosphorinanen; eine neue Möglichkeit zur Knüpfung von S—S-Bindungen / Synthesis and Properties of 3,6-D iorgano-3,6-dithio-1,2,4,5,3,6-tetrathiadiphosphorinanes; a New Possibility of Forming S—S Bonds
Authors: Hahn Josef , Nataniel Tina
Published: March 2015

The six-membered sulfur-phosphorus heterocycles 3,6-diorgano-3,6-dithio-1,2,4,5,3,6-tetrathiadiphosphorinanes (RP(S)S2)2 (R = Me 1a and R = t-Bu 1b ) are formed in high yields from the silyl esters of the corresponding trithiophosphonic acids RP(S)(SSiMe3)2 and dimethylsulfoxide. They are fairly stable in the crystalline state. In solution sulfur elimination occurs, which in the case of l a leads to the formation of 3,5-dimethyl-3,5-dithio-1,2,4,3,5-trithiadiphospholane, MeP(S)S2PMe(S)S (4). Likewise lb decomposes to give the corresponding dithiophosphonic acid anhydride (t-BuP(S)S)2. According to NMR spectroscopic conformational analysis, 1a exists in four isomeric forms: two chair and two twist-boat conformations, which differ in the orientation (cis or trans) of the Me groups. The isomeric distribution indicates that the Me groups prefer the axial positions. As a consequence of steric bulk, 1b is only present in the twist-boat conformation with trans orientation of the t-Bu substituents.
Zur Reaktion von Bis(dimethyIamino)phosphaten mit Antimon(V)chlorid / The Reaction of Bis(dimethylamino)phosphates with Antimony(V) Chloride
Authors: Knödler F. , Schwarz W. , Schmidt A.
Published: March 2015

Potassium bis(dim ethylamino)phosphate monohydrate reacts with antimony(V) chloride to yield the 1:1 adduct 2 of bis(dimethylamino)phosphoric acid and antimony(V) chloride, while anhydrous tetramethylammonium bis(dimethylamino)phosphate affords, in comparison, the dimeric tetrachloroantimony(V) bis(dimethylamino)phosphate (1). The molecular structures of 1 and 2 have been determined by X-ray analysis. The vibrational and mass spectra are reported and briefly discussed.
Ubergangsmetallkomplexe mit Schwefelliganden, XXXIII*/ Transition Metal Complexes with Sulfur Ligands, XXXIII*
Authors: Sellmann Dieter , Binker Gerhard , Knoch Falk
Published: March 2015

In order to investigate the specific properties which are associated with metal sulfur cen­ters, the system Ru/S2C6H4
2- has been studied with respect to the synthesis of new com­plexes and their reactions as well as their structure. cis-(NBu4)(Ru(NO))(PMe4)(S2C6H4)2] reacts with an excess of PMe3 in boiling THF to give the paramagnetic (μeff = 0,96 B. M., 295 K) trans-(NBu4)(Ru(PMe4)2(S2C6H4)2) (I). A plausible intermediate in this reaction is the nitrido complex (NBu4)(Ru(N)(S2C6H4)2) (2) since 2 gives with one equivalent of PMe3 a very labile product which is probably (NBu4)(Ru(N)(PMe4)(S2C6H4)2) (3). but reacts with an excess of PMe3 even at 20 °C to give 1.

The Ru(III) complex 1 is easily oxidized by O2 or PhN2BF4 to yield the diamagnetic Ru(IV) species trans-(Ru(PMe3)2(S2C6H4)2) (4). Remarkably, the transformation of 1 into 4 is achieved also by H+ ions, providing a model reaction for the coupled H+-electron transfer which has been discussed for substrate reactions at metal sulfur centers of enzymes. - The reaction of RuCl2(PMe3)4 with S2C6H4
2- yields [Ru(PMe3)4(S2C6H4)] (5) at 20 °C, even if an excess of S2C6H4
2- is applied. Upon heating in THF or EtOH, 5 looses one PMe3 ligand to give the 16e -complex [Ru(PMe4)4(S2C6H4)] (6) which rapidly coordinates CO to give [Ru(CO)(PMe4)4(S2C6H4)] (7); '1P NMR indicates a meridional coordination of PMe4 in 7, and consequently CO must be trans to S2C6H4
2-. 6 reacts also with LiAlH4 to yield a very sensitive hydride complex to which the tentative formula [Ru(H)2(PMe3)2(S2C6H4)] is assigned. All compounds were characterized by elemental analyses and spectroscopic means, the structures of I and 5 were determined by X-ray structure analysis.
Reaktionen von Silylphosphanen mit Halogenokomplexen von Übergangsmetallen: Synthese, Struktur und Eigenschaften von Komplexen des Typs cis-X(CO)4Mn{PPh3-n(SiMe3)n} (n = 1 -3 ) und [{Cp(CO)2Fe}2PPhR]X (R = Ph, H) bzw. [{Cp(CO)2Fe}3PH]X (X = CI, Br, I) / Reactions of Silylphosphanes with Halogeno Complexes of Transition Metals: Synthesis, Structure and Properties of Complexes cis-X (CO)4 Mn{PPh3-n(SiMe3)n} (n = 1 -3 ), [{Cp(CO)2 Fe}2 PPhR]X (R = Ph, H) and [{Cp(CO)2 Fe}3 PH]X (X = Cl, Br, I)
Authors: Effinger Guido , Hiller Wolfgang , Lorenz Ingo-Peter
Published: March 2015

The reactions of pentacarbonylmanganese halides (CO)5MnX (X = Cl, Br, I) with the silyl- phosphanes Ph3-nP(SiMe3)n (n = 1 -3) at ambient temperature result in the elimination of one CO ligand and the formation of c/s-configurated substitution products X(CO)4Mn{PPh3-n(SiMe3)n). No CO-substitution, but Me3SiX-elimination is observed in the reaction of Ph3-nP(SiMe3)„ with the dicarbonylcyclopentadienyliron halides CpFe(CO)2X to give the di- and triferriophosphonium halides [{Cp(CO)2Fe}2PPhR]X (R = Ph, H) and [{Cp(CO)2Fe}3PH]X (X = Cl, Br, I). The mass, IR and NMR spectra are reported and discussed. The crystal structures of Cis-I(CO)4MnPPh2SiMe3 and [(Cp(CO)2Fe)2PPh2]I have been determined.
Synthese und Struktur des ersten Cyclophosphazens mit einer Metall—Metall-Bindung im Ringgerüst / Synthesis and Structure of the First Cyclophosphazene Containing a Metal —Metal Bond within the Ring Skeleton
Authors: Herbst Regine , Katti Kattesh V. , Roesky Herbert W . , Sheldrick George M.
Published: March 2015

The reaction of [H2NPPh2NPPh2NH2]Cl (1) with WClft (2) proceeds with formation of

(3) and HCl5N6P4Ph8W2 (4). 3 is the main product of this reaction. 4 was characterized by an X-ray structure determination. 4 contains a seven and a six-membered phosphorus-nitrogen ring with a W-W bond of 269.2 pm.
Synthese von Wolframkomplexen des Typs [LW(CO)3X]+ (X = H, F, Br; L = 1,4,7-Triazacyclononan). Die Kristallstrukturen von [LW(CO)3Br]BF4 und [LW(CO)3H]2[WOCl5]·H2O / Synthesis of Tungsten Complexes of the Type [LW(CO)3X]+ (X=H, F, Br; L=1,4,7-triazacyclononane). The Crystal Structures of [LW(CO)3Br]BF4 and [LW(CO)3H]2[WOCl5]·H2O
Authors: Schreiber Peter , Wieghardt Karl , Flörke Ulrich , Haupt Hans-Jürgen
Published: March 2015

The reaction of LW(CO)3 (L = 1,4,7-triazacyclononane) with Br2 in CHCl3 yields orange [LW(CO)3Br](Br3) which was converted to its BF4
- salt. [LW(CO)3Br]BF4 crystallizes in the triclinic space group P1̅ (a = 8.273(3), b = 8.628(2), c = 13.034(3) Å , α = 80.10(2), β = 72.69(2), γ = 61.14(2)°, Z = 2); it consists of cations [LW(CO)3Br]+ , with seven-coordinate W atoms, and BF4
- anions. The corresponding salt [LW(CO)3F](PF6) was obtained from LW(CO)3 with 20% aqueous HF in the presence of air and addition of NaPF6. The analogous reaction with 37% aqueous HCl affords green crystals of [LW(CO)3H]2[WOCl5]·H2O which crystallize in the monoclinic space group P21/c (a = 12.234(4), b = 18.853(7), c = 14.609(5) Å, β = 105.65(3)°, Z = 4). The W atoms in the [LW(CO)3H]+ cations are seven-coordinate; the six-coordinate [WOCl5]2- anions are not disordered. The W = O distance is short (1.72(1) Å ), the mean equatorial W-Cl distance is 2.390 Å whereas the W-Cl bond distance trans to the W = O group is 2.562(5) Å.
Solution Structures of Pyrophthalones, II [1]. Structure and Conformation of Iminopyrophthalone — a High Resolution 1H, 13C, 15N and Solid State 13C-CP/MAS-NMR Study
Authors: Haupt Erhard T. K. , Dieck Heindirk tom , Bontchev Panayot R.
Published: March 2015

The complete analysis of the 1H, 13C, 15N NMR spectra of iminopyrophthalone demonstrates that the solution structure of the molecule must be described as a protonated iminocompound. 13C-CP/MAS spectroscopy proves that the solid state structure of α-PPH and IPH are equivalent to the solution structure.
Mixed Dithizonato-Alkylxanthato Complexes of Ni(II): Spectral, Magnetic, and Thermogravimetric Studies
Authors: Aly Aref A. M. , Kamal Mostafa M. , El-Meligy Mahmoud S. , El-Said Asma I.
Published: March 2015

Mixed ligand complexes of the type Ni(ROCS2)HDz) have been prepared, where R = methyl, ethyl, propyl, butyl and cyclohexyl, and HDz = dithizonate anion. These complexes were identified on the basis of spectroscopic measurements (IR, UV-VIS and NMR), magnetic moment values, thermogravimetric analysis, and analytical data. The results permit assignment of a tetrahedral structure for these complexes.
Über Inhaltsstoffe von Euphorbiaceae, 9. Mitt. [1]. Neue Cerebroside aus Euphorbia biglandulosa Desf. / Constituents of Euphorbiaceae, 9. Comm. [1]. New Cerebrosides from Euphorbia biglandulosa Desf.
Authors: Falsone Gioacchino , Budzikiewicz Herbert , Wendisch Detlef
Published: March 2015

From the latex of Euphorbia biglandulosa Desf. the cerebrosides 1-O-β-D-glucopyranosyl- 2-N-2′-hydroxy-cis-15-tetracosenoyl-4-hydroxy-eicosasphinga-as-10-enine (1), 1-O-β-D-glucopyranosyl- 2-N-2′-hydroxy-cis-17-hexacosenoyl-4-hydroxy-eicosasphinga-cis-10-enine (2) and 1-O-β-D-glucopyranosyl-2-N-2′-hydroxy-4-hydroxy-eicosasphinga-cis-10-enine (3) were isolated. Structures have been elucidated by 1H NMR , 13C NMR . MS spectroscopy, hydrolysis, and ozonolysis, too.
Darstellung und Kristallstrukturen von (PH4P)4Sb8I28 und (Ph4P)Sb3I10(Ph = C6H5) / Synthesis and Crystal Structures of (PH4P)4Sb8I28 and (Ph4P)Sb3I10(Ph = C6H5)
Authors: Pohl Siegfried , Saak Wolfgang , Haase Detlev
Published: March 2015

The compounds (Pn4P)4Sb8I28 (1) and (Ph4P)Sb3I10 (2) were prepared by the reaction of SbI3 and Ph4PI in acetonitrile (molar ratios 2:1 and 3:1 respectively). The structures of 1 and 2 were determined from single crystal X-ray diffraction data.

1 crystallizes in the triclinic space group P1̄ with a - 1321.7(5). b = 1346.7(5), c = 2201.8(8) pm, α = 104.18(2). β = 99.92(2), γ = 100.33(2)°; 2: monoclinic, C2/c, a = 2371.1(2), b = 745.0(1), c = 2495.1(2) pm, β = 100.75(1)°.

Whereas 1 exhibits isolated Sb8I28
4- ions, the anions of 2 are built up of polymeric chains [Sb3I10
- ]∞. In both compounds the distorted Sbl6 octahedra are linked by common edges. The Sb-I distances are in the range between 277.4 and 354.8 pm (1) and between 277.4 and 342.4 pm (2). The observed structures do not only depend on stoichiometry, the nature of the counter cations, and the possibility of oligomerisation but also on the wide variety of the Sb-I bond strengths and the different bridges formed by iodine.

The lone pair of Sb(III) seems to be predominantly 5 s2.
Zur Bildungskinetik des Zeolithen ZSM-11 / On the Kinetics of Formation of the Zeolite ZSM-11
Authors: Hund Matthias C. , Tißler Arno , Polanek Peter , Dräger Martin , Unger Klaus K.
Published: March 2015

The synthesis of pentasil ZSM-11 with Bu4NHSO4 as template was first optimized in a tefloncoated autoclave of 200 ml volume (163 °C, 3 days) and then transferred to a stirring autoclave of 1000 ml volume. The latter allowed sampling over the period of crystallization. Pure ZSM-11 crystallized at temperatures between 150 and 180 °C. In this range the induction period decreased from 15 to 2 hours while the rate of crystallization was enhanced from 2.5 to 5.6% per minute. From these values energies of activation for nucleation and crystallization were determined (99.8 and 43.4 kJ mol-1).
Neuartige basische Liganden für die homogenkatalytische Methanolcarbonylierung, XI [1]. Ether-Phosphan-Cobalt-Komplexe in der katalytischen Methanolhydrocarbonylierung zu Acetaldehyd / Novel Basic Ligands for the H om ogeneous Catalytic Methanol Carbonylation, XI [1]. Ether Phosphane Cobalt Complexes in the Catalytic Hydrocarbonylation of Methanol to Acetaldehyde
Authors: Lindner Ekkehard , Schober Uwe , Glaser Erhard , Norz Hubert , Wegner Peter
Published: March 2015

PhP(CH2C4H7O2)2 (1) and [-CH2(Ph)P~D]2 (3a-c) [D = CH2C4H702 (a), CH2C4H7O (b). CH2CH2OCH3 (c)] are obtained by reaction of Li2PPh and Na(Ph)P~D with ClCH2C4H7O2 and C1CH2CH2Cl, respectively. 1 and 3a, b give rise to high selectivities and conversions in the cobalt catalyzed hydrocarbonylation of methanol to acetaldehyde. Model complexes of cobalt which are of importance in the catalytic cycle are synthesized. Complexes of the type X2Co(Ph2P~D)2 (6az, 6bx-bz, 6cx-cz), especially those with X = I, obtained from CoX2 [X = Cl (x), Br (y), I (z)] and the ether phosphanes Ph2P~D (5a-c), are regarded as precursors of the catalytically active species. With K[HB(sec-C4H9)3] they are reduced to the cobalt(I) complexes XCo(Ph2P~D)(Ph2P~D) (7az, 7bx-bz, 7cx-cz). Trapping reactions with CO, PPh3 or 5b, c lead to the compounds XCo(CO)2(Ph2P~D)2 (8az, 8bx-bz, 8cx-cz), XCoPPh3(Ph2P~D)2 (9bx-bz). and XCo(Ph2P~D)3 (10bz, cz), respectively, with cleavage of a Co-O bond. The reduction of X2Co(PPh3)2 (11x, z) with K[HB(sec-C4H9)3] represents a simple method for the preparation of the complexes XCo(CO)2(PPh3)2 (13x, z) which are formed from the intermediates XCo(PPh3)2 · THF (12x, z) in the presence of CO.
Wechselwirkung des Vanadyl(IV)-Kations mit Nucleotiden in wäßriger Lösung / Interaction of the Vanadyl(IV) Cation with Nucleotides in Aqueous Solution
Authors: Urretavizcaya G. , Baran E. J.
Published: March 2015

The interaction of VO2+ with mono-, di- and trinucleotides and with some of the related nucleosides and bases, was investigated spectrophotometrically at pH = 4.9. The results point to a preferential interaction of the cation with the phosphate groups of all the nucleotides whereas no interaction with the nucleosides and bases was detected. The vanadyl coordination sphere shows some distortive effects in the case of mononucleotides whereas it appears more regular in the case of di- and trinucleotides. At high pH-values the cation interacts with the deprotonated OH-groups of the ribose moieties. This type of interaction was confirmed by direct measurements with pure ribose and ribose-5′-phosphate, and it was absent in the case of thymidine nucleotides, in which ribose is replaced by 2′-deoxyribose.
Verteilung und Valenz der Kationen in Spinellsystemen mit Eisen und Vanadium, V Röntgenographische und Mößbauer-spektroskopische Untersuchung des Spinellsystems FeV2O4—MgV2O4 / Distribution and Valence of the Cations in Spinel Systems with Iron and Vanadium, VX-Ray and Mössbauer Investigation of the Spinel System FeV2O4—MgV2O4
Authors: Riedel Erwin , Alisch Christian
Published: March 2015

In the spinel system FeV2O4-MgV2O4 pure Fe(II)-spinels could not be prepared. Mössbauer spectra show that the solid solution has the composition Fex
2+ Mg1-x[Fey
3+V2-y]O4. with y depend­ing on the partial pressure of oxygen during preparation.
Phosphaniminatokomplexe von Molybdän(V). Die Kristallstruktur von [MoCl4(NPPh3)]2 / Phosphaneiminato Complexes of Molybdenum(V). The Crystal Structure of [MoCl4(NPPh3)]2
Authors: Hosier Klaus , Weller Frank , Dehnicke Kurt
Published: March 2015

[MoCl4(NPPh3)]2 is prepared by the reaction of Mo2Cl10 with Ph3PNSiMe3 in boiling CH2Cl2 as brown paramagnetic (μeff = 1.72 B.M. at 20 °C) crystals, which contain ~2 mol CH2Cl2 per formula unit. With PPh4Cl the yellow complex PPh4[MoCI3(NPPh3)] · CH2Cl2 is formed. The IR spectra are recorded and discussed. [MoCl4(NPPh3)]2 crystallizes monoclinically in the space group P21/n with two formula units per unit cell (3146 observed independent reflexions, R = 0.046). The cell dimensions are a = 981.6; b = 1401.7; c = 1743.1 pm; β = 101.15°. The complex is centrosymmetric dimer showing MoCl2Mo bridges with Mo-Cl bond lengths of 244 and 278 pm. respectively. The Mo=N = P axis is nearly linear (bond angle 168.5°) with bond lengths MoN = 172 pm and PN = 166 pm. which correspond to double bonds.
Mild and Efficient Oxidative Cleavage of N,N-Dialkylhydrazones to Ketones with Sodium Perborate
Authors: Enders Dieter , Bhushan Vidya
Published: March 2015

N,N-Dialkylhydrazones, such as dimethyl- and SAMP-hydrazones, are efficiently cleaved back to their parent ketones under mild conditions at pH 7. The oxidative hydrolysis is effected in good yields with the very cheap bulk chemical sodium perborate in buffer solution and tert-butanol as cosolvent.
Kupfer(I)-chlorid-Addukte von Phosphoraniminen Die Kristallstrukturen von Ph 3 PNPh * CuCl und von 2,3-Bis(triphenylphosphoranylidenamino)maIeinsäure-N-methylimid- Kupfer(I)-chlorid / Copper(I) Chloride Adducts of Phosphoranimines The Crystal Structures of Ph3 PNPh·CuCl and of 2,3-Bis(triphenylphosphoranylideneamino)maleic Acid N-Methylimide Copper(I) Chloride
Authors: Maurer Andrea , Fenske Dieter , Beck Johannes , Strähle Joachim , Böhm Eberhard , Dehnicke Kurt
Published: March 2015

The title compounds Ph3PNPh · CuCl (1) and (Ph3P)2 N2 C4O2 (NMe) CuCl (2) have been prepared by the reactions of CuCl with the corresponding phosphoranimines Ph3PNPh and 2.3-bis(triphenylphosphoranylideneamino)maleic acid N-methylimide, respectively. Both com-plexes were characterized by their IR spectra as well as by crystal structure determinations.

Ph3PNPh · CuCl (1): space group P1, Z = 4, 3639 independent observed reflexions, R = 0.038. Lattice dimensions (18 °C): a = 1047.6; b = 1251.5; c = 1755 pm; α = 103.43°; β = 97.24°; γ = 101.30°. The compound forms monomeric molecules; the asymmetric unit contains two crystallo-graphically independent molecules. The CuCl molecule is bonded via the N atom of the phos-phoranimine. Bond lengths: Cu-N = 189 pm; Cu-CI = 209 pm; bond angle N - Cu - CI = 177°.

(Ph3P)2N2C4O2(NMe) · CuCl (2): space group Pbca, Z = 8, 5611 independent, observed reflexions, R = 0.069. Lattice dimensions (25 °C): a = 1224.3; b = 1962.5: c = 2994.0 pm. The compound forms monomeric molecules with the CuCl molecule bonded via one of the N atoms of the phosphoranimine groups. Bond lengths: Cu - N = 194 pm; Cu-CI = 212 pm; bond angle N-Cu -CI -175°.
Elektronenreiche Olefine, 1 / Electron Rich Olefins, 1
Authors: Hausen Hans-Dieter , Kaim Wolfgang
Published: March 2015

Crystal and molecular structure analysis of the electron rich title compound exhibits an undistorted, yet sterically shielded tetra(primary alkyl)-substituted double bond system with alternating anti-periplanar CH2SiMe3 substituents. The diastereotopic methylene protons have been located and their position correlated to the 1HNMR data and to the ESR hyperfine coupling constants of the corresponding radical cation. In contrast to the highly inert all-carbon derivative, tetraneopentylethene, the more electron-rich and more flexible organosilicon title compound reacts with bromine. Close to orthogonal arrangement between the C-C(H2)-Si planes and the ethene plane ensures effective, fourfold σ/π-hyperconjugation.
DarsteIlung und Schwingungsspektren des 13C- und 18O-Hiarkierten trans-Dioxotetracyanoosmats(VI), [OsO2(CN)4]2- / Preparation and Vibrational Spectra of 13C and 18O Labelled trans-Dioxotetracyanoosmate(VI), [OsO2(CN)4]2-
Authors: Preetz W. , Sartori C.
Published: March 2015

Through careful acidification of the aqueous solution of [OsO2(OH)4]2- in the presence of CN- or 13CN- with acetic acid, [OsO2(CN)4]2- or [OsO2(12CN)4]2- are formed, respectively. The reaction of Os18O4 and tetrabutylammonium cyanide with glacial acetic acid in anhydrous methanol yields [Os18O2(CN)4]2- . The shifts of the infrared and Raman bands of the isotopically labelled complexes are in good agreement with Teller-Redlich calculations. The degenerate E modes, expected for tetragonal symmetry, are split by approx. 15 cm-1, indicating an orthorhombic distortion of the complex ion in the solid state. Therefore, all the observed IR- and Raman frequencies are assigned according to point group D2h. For the complex containing an 18O=Os=18O axis, the symmetry is lowered to C2v, and the rule of mutual exclusion is restricted. This results in a weak absorption in the infrared spectrum of the Raman active symmetric OsO stretching vibration and vice versa a weak band in the Raman spectrum for the antisymmetric infrared active mode.
Erdalkaliquadratate, VI [1] SrC4 O4 · 3H2O, Typ III / Alkaline-earth Squarates, VI [1] SrC4O4 ·3H2O, Type III
Authors: Robl Christian
Published: March 2015

SrC4O4 ·3 H2O, type III. was obtained in an aqueous silica gel besides crystals of SrC4O4-3 H20. type I. X-ray crystal structure analysis showed close relationship to BaC4O4-3H20. but no isotypism. Sr2+ is coord|inated by four water molecules and four oxygen atoms of the squarate dianion. The connection of Sr2+ with C4O4
2- leads to layers. The geometry of C4O4
2- is typical for delocalized π-systems. The Osquarate atoms are not equally bound to Sr2+. One Osquaralc atom (0(4)) is bound to two Sr2+, two (O(1). O(2)) are bound to one Sr2+, respectively, and the fourth Osquaratc atom (0(3)) shows no bonding contact to Sr2+. These differences are compensated for by intermolecular hydrogen bonds which involve O(3) three times, O( I) and O(2) once each, but not O(4).
Ein Chelatligand mit einer -NSSSN-Kette: Bis(oxamido)trisulfan und sein Kupferkomplex / A Chelate Ligand with a -NSSSN-Chain: Bis(oxamido)trisulfane and its Copper(II) Complex
Authors: Brunn Karl , Endres Helmut , Weiss Johannes
Published: March 2015

Bis(oxamido)trisulfane was obtained first as a by-product in the synthesis of 3,4-dihydroxy- 1,2,5-thiadiazole, later in direct syntheses from 3,4-diethoxy-1,2,5-thiadiazole. Reaction with anhydrous CuCl2 gave bis(oxamido)trisulfane copper(II). Bis(oxamido)trisulfane is monoclinic P21/n, a = 8.975(2) A. b = 8.875(1) Å, c = 12.781(2) Å. β = 94.40(2)°, V = 1015.05(4) Å3, Z = 4, Mr = 270.31, Dx = 1.76 g cm-3, MoKα,λ = 0.7107 Å, μ = 7.0 cm-1 , wR = 0.038 for 1371 observed independent reflections.

Bis(oxamido)trisulfane copper(II) is triclinic PI, a = 5.279(1) Å, b = 11.388(3) Å, c = II.943(4) Å, a = 89.08(2)°, β = 82.62(2)°, γ = 86.44(2)°, V = 710.8(3) Å3, Z = 2, Mr = 331.83, Dv = 1.56 gcm-1, MoKα,λ =0.7107 Å, μ = 19.89 cm-1, wR = 0.039 for 1974 observed independent reflections.
Radical Ions, 78 [1, 2] The Oxidative Desulfuration of Organic Cyclic Polysulfides to Disulfide Radical Cations in AlCl3 /H2 CCl2 Solution
Authors: Bock H. , Chenards B. L. , Rittmeyer P. , Stein U.
Published: March 2015

Organodisulfide radical cations R2S2'® and R2C2S2'® can be generated from aliphatic as well as aromatic cyclic polysulfides in A1C13/H2CC12 solutions and characterized by their ESR spectra. Examples presented are the oxidations of 1,2,3-trithiolanes to 1,2-dithiolane radical cations, in which energetically favored planarized 3 electron/2 center bonds - S a r e formed.
Die Kristallstruktur von Calciumhexacyanoferrat(II)- Hexamethylentetramin-Wasser(1/1/6) Ca2 [Fe(CN)6] · C6H12N4 · 6H2O / The Crystal Structure of Calciumhexacyanoferrate(II)- Hexamethylenetetramine-Water(1/1/6) Ca2[Fe(CN)6] · C 6H12N4 · 6H2O
Authors: Meyer H.-Jürgen , Pickardt Joachim
Published: March 2015

Ca2[Fe(CN)6] · C6H12N4 · 6H2O crystallizes in the monoclinic space group B2/b with a = 1130,2(4), b = 1373,5(4), c = 1353,0(4) pm and γ = 97,17°. The X-ray single crystal structure determination converged at R = 0.055 (2057 reflections). Each of the four Fe(CN)6 octahedra (Z = 4) in the unit cell is coordinated by six Ca atoms with mean NCYAN - Ca distances of 253.5(3) pm. The Ca atoms are bridged by hexamethylenetetramine and water molecules
Untersuchungen an Polypseudohalogeniden, V[1] Darstellung und Kristallstruktur des Kaliumdicyanoiodats(I), K[I(CN)2] / Studies on the Polypseudohalides, V [1] Preparation and Crystal Structure of K[I(CN)2]
Authors: Tebbe Karl-Friedrich , Krauß Norbert
Published: March 2015

The new compound K[I(CN)2] can be prepared by addition of one formula unit of iodine to a concentrated aqueous solution of two mole equivalents of potassium cyanide. It crystallizes in the monoclinic space group C2/m with a = 736.4, b = 451.4, c = 908.0 pm, β = 92.56° and Z = 2. The crystal structure has been refined to Rf = 0.020 for 301 observed reflections.

The structure may be described as a layer-like package of cations K+ and trihalide-analogous anions [I(CN)2]-. The anions are strictly linear at the I atoms (symmetry 2/m) and nearly linear at the C atoms with φ (I-C-N) = 178.6° and d(I-C) = 229.8, d(C-N) = 112.9 pm. The cation is surrounded by a slightly distorted octahedron of nitrogen atoms with d(K···N) = 284.8,292.6 pm
Zur Existenz diskreter TeCl-
5 -Ionen / On the Existence of Discrete TeCl-
5 Ions
Authors: Schönherr Thomas
Published: March 2015

Discrete mononuclear TeCl-
5 anions were prepared for the first time in solid phase in association with bulky cations as tetrabutylammonium and tetraphenylphosphonium. The vibrational spectra imply tetragonal symmetry as for the isoelectronic TeF-
5 anion which is caused by a stereochemically active lone pair. A complete vibrational assignment is given and supported by a normal coordinate treatment for both ions. The significance of the resulting force constants is briefly discussed
Iodomanganate(II): Darstellung und Kristallstrukturen von (Ph4P)MnI3L, MnI2 L3, [MnIL5]I3 und [MnL6](I3)2 (L = Tetrahydrofuran) / Iodomanganates(II): Synthesis and Crystal Structures of (Ph4P)MnI3L, MnI2L3, [MnIL5]I3 and [MnL6](I3)2
Authors: Stolz Peter , Pohl Siegfried
Published: March 2015

The compounds (Ph4P)MnI3L (1), MnI2L3 (2), [MnIL5]I3 (3), and [MnL6](I3)2 (4) (L = C4 H8O, thf) were prepared in thf solution and their structures determined from single crystal X-ray diffraction data. 1 crystallizes in the monoclinic space group C2/c with a = 1743.6(1), b = 1985.8(1), c = 1806.7(1) pm, β = 98.74(1)°, Z = 8. The structure of 1 exhibits tetrahedral anions. The Mn-I distance was found to be 268.0 pm (mean). 2: monoclinic, C2/c with a = 1252.3(2), b = 1255.0(3), c = 1271.8(3) pm β = 113.88(2)°, Z = 4. The characteristic feature of the structure of 2 is the existence of neutral MnI2L3 molecules with a distorted trigonal bipyramidal geometry and the iodine atoms in equatorial positions (Mn-I: 271.1 pm). The compound crystallizes from a solution of Mnl2 in tetrahydrofuran. 3: monoclinic, C2/c with a = 1695.3(1), b = 1123.1(1), c = 1646.2(1̱) pm, β = 96.91(1)°, Z = 4. The preparation of 3 from 2 and iodine yields octahedral MnIL+
5 cations (Mn-I: 278.8̄ pm) and triiodide anions. 4: monoclinic, P21/n with a = 1005.5(1). b = 1056.8(1), c =1835.6(2) pm, β = 91.16(1)°, Z = 2. 4 is prepared from 3 and iodine in thf solution, and shows octahedral MnL6
2+ cations and triiodide anions
Phasengleichgewichte und intermediäre Phasen im System Al–Te / Phase Relations and Intermediate Phases in the Al–Te System
Authors: Kniep Rüdiger , Blees Peter
Published: March 2015

The binary system Al-Te contains the intermediate phases AlTe (m.p. 857 °C, syntectic). Al2Te3 (α-phase stable up to 720 °C; β-phase: m.p. 903 °C, congruent) and Al2Te5 (stable between 415 °C and 465 °C, incongruent). The crystal structure of α-Al2Te3 is monoclinic (super-structure; a = 41.565(8) Å, b = 7.189(1) Å, c = 25.477(7) Å, β = 90.21(2)°. Z = 48. Dx = 4.57g/cm3). Te positions of the sub-cell (monoclinic P21; a/3, b, c/6, β) were determined by direct methods; Te atoms are arranged in close-packed layers which are stacked along [100] with the sequence ABCBA. A metastable cubic phase of composition Al2Te3 (Zinc blende-type-structure; a = 5.949(1) Å; Al with random distribution) is obtained by thermal decomposition of ternary compounds AlTeX (X = Cl, Br, I)
Trimethylsilylphosphite und Hexafluoraceton: Phosphonate versus Dioxaphospholane — 1:1- und/oder 1:2-Addukte / Trimethylsilylphosphites and Hexafluoroacetone: Phosphonates versus Dioxaphospholanes —1:1 and/or 1:2 Adducts
Authors: Heine Joachim , Röschenthaler Gerd-Volker
Published: March 2015

The [2,2,2-trifluoro-1-(trifluoromethyl)-1-(trimethylsiloxy)ethyl]phosphonates 2a-g and/or the 4,4,5,5-tetrakis(trifluoromethyl)-1,3,2λ5σ4-dioxaphospholanes 4a-c, e were obtained from the silylphosphites 1a-g and hexafluoroacetone depending on the reaction conditions. Intermediates were the λ5σ5-phosphoranes 3a-e formed by an 1:2 oxidative addition of hexafluoroacetone whereas in the case of the cyclic phosphites 1f and g thermally stable phosphoranes, 3f, 6 and 3g were found to undergo no substituent exchange
Substituierte Heptaarsane(3) As7(Mme3)3 (M = Si, Ge, Sn) mit Nortricyclenstruktur / Substituted Heptaarsanes(3) As7(Mme3)3 (M = Si, Ge, Sn) with Nortricyelene Structure
Authors: Hönle Wolfgang , Wolf Juliane , Schnering Hans Georg von
Published: March 2015

The heptaarsanes(3) As7(Mme3)3 (M = Si, Ge, Sn) with nortricyclene structure have been synthesized by heterogeneous and homogeneous reactions from K3As7 and Rb3As7, respectively, with Mme3Cl. The crystal structures have been determined. The compounds are isotypic and crystallize in unit cells of R3̄̄ symmetry, containing pairs of enantiomers. The bond lengths d(As-As) in the nortricyclene skeleton are nearly uneffected by the substituents and show the sequence typical for covalent nortricyclenes: d(basal) = 244.3 pm > d(basal-equatorial) = 242.7 pm > d(equatorial-apical) = 240.7 pm (mean values). The spread-off of the Mme, substituents decreases as going from P7 to As7 skeletons as well as with increasing size of M
Darstellung eines cyclischen Ferrocenderivates mit Wolfram (VI) / Preparation of a Cyclic Ferrocene Derivative of Tungsten(VI)
Authors: Roesky Herbert W. , Swarat Karsten , Edelmann Frank
Published: March 2015

Ph2PC5H4FeC5H4PPh2 (1) reacts with Me3SiN3 with evolution of nitrogen to yield (Me3SiN = PPh2C5H4)2Fe (2). Treatment of 2 with WF6 results in the formation of (C5H4PPh2N)2FeWF4 (3). 3 is a rare example of a metal complex containing two metal atoms in very different oxidation states
Studies on Enteric Anthelmintics: Impact of Single Point Structural Change on the Activity Profile
Authors: Khan A. M. , Gupta Suman , Katiyar J. C. , Akhtar M. Shamim , Sharma V. L. , Bhaduri A. P.
Published: March 2015

The impact of change only in one heteroatom in the substituent at position 5(6) of methyl benzimidazole-2-carbamates on the profile of anthelmintic activity against intestinal worms Ancylostoma ceylanicum (hookworm), Nippostrongylus brasiliensis (trichostrongylid), Syphacia obvelata (oxyurid) and Hymenolepis nana (cestode) has been studied. The observations made are likely to evoke interest for understanding the SAR in methyl benzimidazole-2-carbamates anthelmintics at a molecular level
Darstellung und Kristallstruktur von Zinkazid · 4-Methylpyridin / Preparation and Crystal Structure of Zinc Azide · 4-Methylpyridine
Authors: Mautner Franz A. , Krischner Harald , Kratky Christoph
Published: March 2015

Zinc azide · 4-methylpyridine (1) is formed by the reaction of zinc azide with the corresponding pyridine in aqueous solution. The crystal structure was determined by single crystal X-ray diffraction methods. The crystals of 1 are monoclinic, space group C2/c, Z = 4, a = 1085.5(2), b = 1692.7(11), c = 619.7(6) pm, β = 113.47(5)°. Each zinc atom is surrounded by five nitrogen atoms (four from azide groups and one from the pyridine adduct) in a distorted trigonal bipyramidal fashion. The ZnN5-polyhedra share common edges to form chains along the crystallographic c-axis.
Koordination des dreizähnigen makrocyclischen Liganden 1-Thia-4,7-diazacyc!ononan an Palladium(II) und Platin(II) / Coordination of the Tridentate Macrocyclic Ligand 1-Thia-4,7-diazacyclononane to Palladium(II) and Platinum(II)
Authors: Hoffmann Peter , Mattes Rainer
Published: March 2015

The reaction of PdAc2 and K2PtCl4 with the ligand 1-thia-4,7-diazacyclononan (C6H14N2S - L) yield crystals of [PdL2](PF6)2 (4) and [PtL2]Br2-H2O (5), respectively. The structures of 4 and 5 have been determined.

Crystal data: 4, monoclinic, space group P21/c, a = 719.2(1), b = 1712.5(3), c = 936.8(2) pm. β = 99.15°, Z = 2; 1708 reflections, R = 0.029.

5, monoclinic, space group P21/c, a = 1682(2). b = 786(1), c = 1573(1) pm. β = 108.1(1)°, Z - 4; 1706 reflections, R = 0.070. 4 contains octahedrally coordinated Pd(II); in addition to the square planar PdN4 group (mean Pd -N bond length 206 pm) the S-donor atoms are weakly coordinated in the axial positions (Pd-S: 303.4(1) pm). In 5, however, Pt(II) is in a square planar ligand environment. The S-donor atoms are bent away from the axial positions of the central atom.
The Thermal Decomposition of Ammonium Metavanadate(V) in Open and Closed Systems
Authors: Range Klaus-Jürgen , Zintl Reinhard , Heyns Anton M.
Published: March 2015

The thermal decomposition of ammonium metavanadate(V) has been studied at atmospheric pressure, at hydrothermal, and high-pressure conditions, respectively. In a closed high-pressure system a redox reaction between vanadium(V) and ammonia takes place, to yield with increasing temperature the compounds (NH4)2V6O12(OH)2, VO2-δ(OH)δ, and V2nO2n-1 the composition of the product eventually approaching V2O3 at 1100 °C. All these compounds can easily be converted into V2O5 by heating in air. The mid-infrared spectra of the decomposition products obtained by slow heating of NH4VO3 in air, are virtually identical and show that ammonium hexavanadate(V), (NH4)2V6O16, is the most important, and perhaps only, intermediate in the “non-reduction” case. On further heating, (NH4)2V6O16 may not only loose ammonia and water to form V2O5 but could as well partially be reduced by ammonia. This could explain the diversity of intermediate “compounds” described in the literature. Hydrothermal reaction of NH4VO3 yielded (NH4)0.5V2O5, (NH4)2V3O8, and V2O3 at rather low temperatures.
Pseudohalogeno-Metallverbindungen, LXVIII [1]. Reaktionen der Cyanometallsäuren NCAuCNH, (NC)4Pt(CNH)2, (NC)2M(CNH)4(M = Fe, Ru, Os) und Co[bis(dimethyIglyoximato)](CN)CNHmit Epoxiden: 2-Hydroxyalkylisocyanid- und Oxazolidin-2-yIiden-MetalIkomplexe / Pseudohalogeno Metal Compounds, LXVIII [1]. Reaction of Cyano Metal Acids NCAuCNH, (NC)4Pt(CNH)2, (NC)2M(CNH)4 (M = Fe, Ru, Os) and Co[bis(dimethylglyoximato)](CN)CNH with Epoxides: 2-Hydroxyalkylisocyanide and Oxazolidine-2-ylidene Metal Complexes
Authors: Weigand Wolfgang , Nagel Ulrich , Beck Wolfgang
Published: March 2015

NCAuCNH reacts with expoxides to give oxazolidine-2-ylidene (2) and 2-hydroxyalkyl complexes (3), respectively. Complexes with cyclic carbene ligands [XXX] (5) and [XXX] (7) are formed from the corresponding isocyanic metal compounds and oxiranes. 5b has been characterized by crystal structure determination. Ring opening of phenyloxirane occurs at the phenyl substituted carbon atom. (NC)2M(CNH)4 (M = Fe, Ru, Os) and oxirane yield mixtures of [XXX] and [XXX].
Reaktionen mesoionischer Fünfringheterocyclen mit o-chinoiden Verbindungen, VII [1]. Thermische [π4+π4]-Cycloadditionen eines bicyclischen Imidazolo[1,2-c]thiazolsystems / Reactions of Mesoionic Five-Membered Heterocycles with o-Quinoid Compounds, VII [1]. Thermal [π4+π4]Cycloadditions of a Bicyclic Imidazolo[1,2-c]thiazole System
Authors: Friedrichsen Willy , König B.-Michael , Debaerdemaeker Tony
Published: March 2015

5-(4-Methylphenyl)-2,7-diphenyl-4-phenylcarbamoylimidazolo[1,2-c]thiazol (9) reacts with tetrachloro-o-benzoquinone to give a [π4+π4]cycloadduct (17); in an obviously analogous manner 5-(4-methylphenyl)-2.7-diphenylimidazolo[1,2-c]thiazol (8) with N, N′-benzenesulfonyl-obenzoquinonediimine (14) yields compound 16 and benzenesulfinic acid. The [π4+π4]adduct 17 solvolyzes with alcohols in a stereoselective SN2″ reaction giving 24a, b. The stereochemical outcome of this reaction has been determined by an X-ray analysis of 24a.
Reaktive E=C(p—p)π-Systeme, XVI [1] Trimethylstannvlphosphane des Typs Me3SnP(R)CF3 (R = Me, Et) als Phosphaalken-Vorstufen / Reactive E=C(p-p)π-Systeme, XVI [1] Trimethylstannylphosphanes of the Type Me3SnP(R)CF3 (R = Me, Et) as Phosphaalkene Precursors
Authors: Grobe Joseph , Szameitat Jürgen
Published: March 2015

Stannylphosphanes of the type Me3SnP(R)CF3 [R = Me (1), Et (2)] have been prepared by a multistep synthesis (Fig. 1) starting either with F3CPI2 or with P(NEt2)3. Due to the alkyl sub­stituents, 1 and 2 show a higher thermal stability than the analogous perfluoroalkyl compounds Me3SnP(RF)2 (RF = CF3, C2F5). Pyrolysis of 1 and 2 at 380 °C/10-3 Torr gives the new phosphaalkenes RP=CF2 (R = Me, Et) as reactive intermediates collected at -196 °C. They polymerize on the attempt to prepare diluted solutions even at very low temperatures. In case of the ethyl derivative the product (EtPCF2)x is a colourless polymer which on heating (500-600 °C) yields a mixture of dimers (EtPCF2)2 (trans-, cis-1,3- and trans-1,2-diphosphetane; ratio 73:13,5:13,5). 1 and 2 have been used as equivalents of the phosphaalkenes RP=CF2 in one-pot reactions with 2,3-dimethylbutadiene and 1,3-cyclohexadiene, respectively. The labile P=C intermediates pro­duced at 120 °C are captured by the dienes affording the [2+4]-cycloadducts 3-6 in good yields. Oxidation with sulfur gives the corresponding phosphane sulfides 7-10 in almost quantitative yields. New compounds were characterized by spectroscopic (NMR, MS, IR) and analytical methods.
Synthese und Struktur von Trichloro(phthalocyaninato)tantal(V) / Synthesis and Structure of Trichloro(phthalocyaninato)tantalum(V)
Authors: Gingl Franz , Strähle Joachim
Published: March 2015

The reaction of TaCl5 with phthalodinitrile at 240 °C yields TaCl3(pc). It crystallizes in the triclinic space group P1̄ with the lattice constants a = 836.0(2), b = 1207.7(4), c = 1368.8(4) pm, α = 79.86(3)°, β = 93.34(2)°, γ = 100.97(2)°, Z = 2. The structure is closely related to that of triclinic TiCl2(pc). In TaCl3(pc) the Ta atom has the coordination number seven. The plane of the three Cl atoms is parallel to the plane of the phthalocyaninato ligand forming a coordination polyhedron of the type square base - trigonal cap with the symmetry Cs. The distances Ta-Cl range from 237.4 to 246.6 pm and the distances Ta-N from 216.7 to 218.8 pm.
Zur strukturellen Verzerrung von Fe4S4I4
2- -Clustern durch Iod-Iod-Kon Die Kristallstrukturen von (Ph4P)2Fe4S4I4 und (Me3NCH2Ph)2Fe4S4I4 / Structural Distortion of Fe4S4I2
2- Clusters through Iodine-Iodine Contacts: Crystal Structures of (Ph4P)2Fe4S4I4 and (Me3NCH2Ph)2Fe4S4I4
Authors: Pohl Siegfried , Saak Wolfgang
Published: March 2015

The structures of (Ph4P)2Fe4S4I4 (1) and (Me3NCH2Ph)2Fe4S4I4 (2) were determined from single crystal X-ray diffraction data.

1 crystallizes in the tetragonal space group I41/a with a = 1088.3(1) and c = 4540.3(2) pm. Z = 4.

2: Monoclinic, space group Cc. a = 1332.0(2), b = 1513.8(3), c = 1755.1(3) pm, β = 96.69(1)°, Z = 4.

In 1 the anion Fe4S4I4
2- has imposed S4 symmetry with four short (226.2 pm) and eight long (228.1 and 228.4 pm) Fe-S distances parallel and perpendicular, respectively, to the crystallo­graphic 4̃ axis. The Fe-Fe distances were found to be 274.3 and 275.5 pm (Fe-I 254.1 p0m).

In (Me3NCH2Ph)2Fe4S4I4 the [Fe4S4]2+ cluster also exhibits a slightly compressed tetragonal core structure but the core distortions are larger and less regular than in 1 (Fe-S distances from 224.6 to 232.9 pm, Fe-Fe distances from 269.6 to 275.9 pm, Fe-I distances from 249.5 to 255.7 pm).

In addition there are in 2 iodine-iodine interactions between the anions with an I-I distance of 391.7 pm. These weak attractive forces seem to be the reason for the rather large and hitherto in [Fe4S4] clusters with four identical ligands unobserved distortion of the Fe4S4 core.
Crystal Structure and Magnetic Property of the Binuclear Manganese(III) Complex with μ-Acetate and Di-μ-Alkoxo Bridges
Authors: Nishida Yuzo , Oshino Naoko , Tokii Tadashi
Published: March 2015

Binuclear manganese(III) complex, [Mn2L(μ-OCH3)(μ-CH3COO)(OHCH3)]ClO4 was pre­pared and characterized in terms of crystal structure determination, magnetic measurement, and ESR spectroscopy, where H3L represents the Schiff base derived from salicylaldehyde and 1,5- diamino-3-pentanol.
Mercuric Oxide-Iodine Oxidation of 6β-Hydroxypregnanes. Influence of the C-5 Functionality
Authors: Brachet-Cota Adriana L. , Burton Gerardo
Published: March 2015

Oxidation of 6β-hydroxyprogesterone and 3β-acetoxy-5 α,6 β-dihydroxypregnan-20-one with mercuric oxide-iodine under photolytic conditions rendered 4α-iodo-5β,6β-oxidopregnan-3,20-dione and 3β-acetoxy-7-iodo-19-formyloxy-5,7-seco-6-norpregnan-5,20-dione respectively.
Beiträge zur Chemie des Bors, 189 [1]. Die Kristall-und Molekülstruktur von Bis(1,3-dithiaborolan-2-yl)sulfid / Contributions to the Chemistry of Boron, 189 [1]. The Crystal and Molecular Structure of Bis(1,3-dithiaborolan-2-yl)sulfide
Authors: Nöth H. , Pommerening H. , Staudigl R.
Published: March 2015

The structure of the title compound has been determined by X-ray diffraction. The molecule has C2 symmetry, containing two dithiaborolanyl groups in twist conformation. The normals of the two BS3 planes of the molecules form an angle of only 17,6°. All BS bonds can be considered to be single bonds.
Synthese und Kristallstruktur von [l,3-Bis(4-ethoxyphenyl)triazenido]pyridino-silber(I), einem dimeren Komplex mit kurzem Silber-Silber-Kontakt / Synthesis and Crystal Structure of [1,3-Bis(4-ethoxyphenyl)triazenido]pyridino Silver(I), a Dimeric Complex with a Short Silver-Silver Contact
Authors: Hartmann Edmund , Strähle Joachim
Published: March 2015

1,3-Bis(4-ethoxyphenyl)triazenido silver(I) (1) is obtained from equimolar amounts of the triazenido anion and AgNO3 in THF/CH3CN. 1 forms in pyridine the dimer [Ag(EtOC6H4NNNC6H4OEt)·py]2 (2) which crystallizes as yellow pyridine solvate 2·2 py in the monoclinic space group P21/n and a = 1067.1(7), b = 1764.5(9), c = 1373.0(9) pm, β = 106.46(7)°, Z = 2. In the centrosymmetric dimer 2, two triazenido ligands bridge two Ag(I) atoms with their atoms N1 and N3 forming an eight-membered heterocycle Ag2N6 with a short Ag-Ag interaction of 272.6 pm. To each Ag atom an additional pyridine ligand is weakly coordinated with a distance Ag-N40 = 245.5 pm. The bond axis N1 - Ag-N3′ within the heterocycle is not linear (158.5°). The Ag-N distances to the N-atoms of the triazenido ligand are 217.6 and 218.5 pm.
Synthese und Struktur von Cäsium-1,5-bis(p-tolyl)pentaazadienid, Cs+(tolN5tol)- / Synthesis and Structure of Cesium 1,5-Bis(p-tolyl)pentaazadienide, Cs+(tolN5tol)-
Authors: Schmid Raimund , Beck Johannes , Strähle Joachim
Published: March 2015

Cs+(tolN5tol)- (1) is formed as a yellow crystalline precipitate after addition of a concentrated aqueous solution of CsCl to a concentrated solution of 1,5-Bis(p-tolyl)pentaazadiene(1,4) in ammonia. 1 crystallizes in the orthorhombic space group Pccn with a = 3169(1), b = 434.3(2), c = 1109.4(7) pm, Z = 4. The structure contains (tolN5tol)- anions and Cs+ cations both occupying two-fold axes. The all-trans N5 zigzag chain is planar with localized double bonds N1 - N2 and N2′ - N1′ of 127.7 pm and shortened single bonds N2-N3 and N3-N2′ of 136.9 pm. The tolyl substituents are titled by 25.5° against the plane of the N atoms. Cs+ is surrounded in a square antiprismatic arrangement by eight N atoms of four N5 chains with distances Cs-N in the range of 314.6 to 366.2 pm.