bluuebunny/crossref_metadata_2025 huggingface dataset:
1,2- und 1,1-Diborylalkene / 1,2- and 1,1-Diborylalkenes
Authors: Siebert Walter , Hildenbrand Manfred , Hornbach Pia , Karger Gerhard , Pritzkow Hans
Published: March 2015

Reactions of B2Cl4 with 3-hexyne, 2,2-dimethyl-3-butyne, and 2,2,5,5-tetramethyl-3-hexyne lead to the cis-bis(dichloroboryl)alkenes la—c; with bis(trimethylsilyl)acetylene geminai diborylation and Me3Si migration occurs to yield (Me3Si)2C=C(BCl2)2 (2a). On heating 2a in benzene a Cl/Me exchange with formation of 2b is observed. Me2C=C(BCl2)2 (4a) is obtained from Me2C=C(SnMe3)2 and BCl3. In 1a—c, e, 2a, and 4a reaction of one Cl of each BCl2 group with Me3Si—NMe2 or iPr2NH leads to the corresponding bis(chloro-dialkylaminoboryl)ethenes 5c, f—i, 5′a, b, e, 2d, e, and 4b, c, of which 5′a, b, e possess the 1-azonia-2-borata-5-borole structure via an intramolecular donor-acceptor N→B bond. 2,4-Bis(t-butyl)-1,3-bis(dimethylamino)-1,3-dihydro-1,3-diborete (6c) is cleaved with bromine to yield the cis-1,2-diborylethene derivative 5j, as established by an X-ray structure analysis.
Trimethylblei-Lithium in Tetrahydrofuran: Synthese von Trimethyl(trimethylplumbyl)silan und des Trimethylplumbyltrihydridoborat-Anions / Trimethyllead-Lithium in Tetrahydrofuran: Synthesis of Trimethyl(trimethylplumbyl)silane and of the Trimethylplumbyltrihydridoborate Anion
Authors: Wrackmeyer Bernd , Horchler Klaus
Published: March 2015

Solutions of trimethyllead-lithium, [Me3Pb]Li (1), in tetrahydrofuran (THF) (-0.5 M) can be obtained from trimethyllead bromide and an excess of lithium at –78°C. 1H. 13C and 207Pb NMR are used for monitoring the formation of the reagent. Extensive decomposition into lead and tetramethyllead is observed at –20°C within minutes. The application of this reagent is demonstrated by the synthesis of trimethyl(trimethylplumbyl)silane (2) and by its stoichiometric 1:1 reaction with BH3–THF at –78°C, leading to lithium trimethylplumbyltrihydridoborate [Me3PB–BH3]Li (3). The composition of the products in solution follows conclusively from their 1H, 11B13C, 29B, 13C, 29Si, and 207Pb NMR data. The silane 2 decomposes slowly at ambient temperature into Me4Si, Me4Pb and lead. The borate is even less stable, decomposing at temperatures above –30°C mainly into lead, Me4Pb, [H4B]Li and [Me4B]Li.
Neutronenbeugungsmessungen an Li2CrCl4 / Neutron Diffraction Studies of Li2CrCl4
Authors: Kuske Peter , Cockcroft Jeremy Karl , Lutz Heinz Dieter
Published: March 2015

Neutron diffraction studies of Li2CrCl4 at 350 °C are presented. The cubic high-temperature polymorph of Li2CrCl4 (space group Fd3̅m, Z = 8, R = 3.26%) crystallizes in an inverse spinel structure (cF56) with large Frenkel disorder of the tetrahedrally coordinated lithium ions. The occupation of the interstitial octahedral 16c sites by lithium ions is 38%, that of the tetrahedral 8a lattice sites only 24%. This large disorder is obviously the reason of the high ionic conductivity of Li2CrCl4 at elevated temperatures. There are some indications of a dynamic Jahn-Teller distortion of the CrCl6 units.
Synthese neuer µ-1,4-Diboracyclohexadien-Tripeldecker-Komplexe [1] / Synthesis of New μ-1,4-Diboracyclohexadiene Triple-Decker Complexes [1]
Authors: Wörner Karl-Fred , Siebert Walter
Published: March 2015

1,2,3,4-Tetramethyl-1,4-diboracyclohex-2-ene (1) reacts in THF solution with two equivalents of potassium metal to yield a red solution of the dianion 12-. Reactions of 1·2 K with allylnickel bromide dimer, cyclooctadiene-rhodium chloride dimer or bis(ethene)rhodium chloride dimer give the triple-deckers 3, 4, and 5, respectively. The constitution of the diamagnetic (30 VE) triple-deckers is derived from NMR and MS data.
Darstellung, Schwingungsspektren und Normalkoordinatenanalyse von Chloro-Bromo-Rhodaten(III) / Preparation, Vibration Spectra and Normal Coordinate Analysis of Chloro-Bromo-Rhodates(III)
Authors: Preetz W. , Kuhr W.
Published: March 2015

The mixed chloro-bromo-rhodates(III) [RhClnBr6-n]3-, n = 1-5, have been separated for the first time by ion exchange chromatography on diethylaminoethyl-cellulose. Due to the stronger trans-effect of Br, as compared with Cl, on treatment of [RhBr6]3- with conc. HCl nearly pure cis/fac-isomers for n = 2, 3, 4 are formed. The reaction of [RhCl6]3- with conc. HBr yields mixtures of the cis/trans-isomers for n = 2, 4, which cannot be separated, but mer-[RhCl3Br3]3 is formed stereospecifically. The IR and Raman spectra of all isolated mixed ligand complexes are completely assigned according to point groups Oh, D3d, C4v, C3v and C2v, supported by normal coordinate analyses based on a general valence force field. The good agreement of calculated and observed frequencies confirms the assignments. Due to the stronger trans-influence of Br as compared to Cl, in all asymmetric Cl—Rh—Br axes the Rh—Br bonds are strengthened and the Rh—Cl bonds are weakened, indicated by valence force constants for Rh—Br approximately 14% higher, for Rh—Cl 10% lower, as compared with the values calculated for symmetric Br—Rh—Br and Cl—Rh—Cl axes, respectively.
Über das 1-Ethyl-2,4,5-triacetylbenzol / On the 1-Ethyl-2,4,5-triacetylbenzene
Authors: Riemschneider Randolph , Buchlow Gerhard , Wons Thomas
Published: March 2015

The preparation and properties of 1-ethyl-2,4,5-triacetylbenzol are discribed. NMR and MS data are given.
Synthese von 1,2,3,4,5-Pentaisopropylcyclopentadien und 1,3,5-Tri-tert-butylcyclopentadien / Synthesis of 1,2,3,4,5-Pentaisopropylcyclopentadiene and 1,3,5-Tri-tert-butylcyclopentadiene
Authors: Sitzmann Helmut
Published: March 2015

Alkylation of tetraisopropylcyclopentadienyllithium (4b) gives a mixture of pentaisopropylcyclopentadiene isomers (1) which on metalation yields 11% pentaisopropylcyclopentadienylsodium (2). The mixture of products obtained on reacting 1,3-di-tert-butylcyclopentadienylsodium (6) with tert-butyliodide can be separated into 80% di-tert-butylcyclopentadiene and 9% 1,3,5-tritert-butylcyclopentadiene (7) by distillation.
Reaktionen 4,4-Bis(trifluormethyl)-substituierter Heterodiene mit Alkinen / Reactions of 4,4-Bis(trifluoromethyl) Substituted Heterodienes with Alkynes
Authors: Burger Klaus , Sewald Norbert , Huber Erasmus , Ottlinger Ralph
Published: March 2015

4,4-Bis(trifluoromethyl) substituted 1-oxa-3-azabuta-1,3-dienes (1) and alkynes react to give open-chain trifluoromethyl substituted N-propargylic amides (4), 4H-1,3-oxazines (5) and 2-oxazolines (6, 7), respectively. The selectivity of the reaction can be controlled effectively by the reaction conditions used.
Darstellung und spektroskopische Charakterisierung von primären und sekundären Sulfoniumsalzen [1] / Preparation and Spectroscopic Characterization of Primary and Secondary Sulfonium Salts [1]
Authors: Minkwitz Rolf , Gerhard Volker , Norkat Thomas
Published: March 2015

The preparation and spectroscopic characterization of the sulfonium salts R2SH+MF6- and RSH2
+MF6- (R = CH3, t-C4H9; M = As, Sb) is reported. The compounds are synthesized by protonation of the corresponding sulfanes in the superacid system HF/MF5.
Ν,N′-Di(t-butyl)-S-ferrocenyl-sulfinsäureimidamid — ein neuer Ligand für die Synthese von Metallkomplexen / N,N′-Di(t-butyl)-S-ferrocenylsulfinic Acid Imidoamide - a New Ligand for the Synthesis of Metal Complexes
Authors: Roesky Herbert W. , Grünhagen Anne , Edelmann Frank T. , Noltemeyer Mathias
Published: March 2015

N-Lithio-N,N′-di(t-butyl)-S-ferrocenylsulfinic acid imidoamide (1) has been synthesized from C5H5FeC5H4Li and Bu′NSNBu′. Treatment of 1 with SnCl4 results in the formation of C18H27Cl3FeN2SSn (2), an orange solid containing a four-membered SN2Sn ring. Complex 2 crystallizes in the monoclinic space group P21/c with cell constants a = 1035.7(5), b = 1403.7(7), c = 1591.5(8) pm; β = 92.79(3)°.
[Na-15-Krone-5] [ReF2Cl2(NO)2]; Synthese, IR-Spektrum und Kristallstruktur / [Na-15-Crown-5][ReF2Cl2(NO)2]; Synthesis, IR Spectrum, and Crystal Structure
Authors: Vogler Stefan , Dehnicke Kurt , Fenske Dieter
Published: March 2015

[Na-15-crown-5][ReF2Cl2(NO)2] has been prepared by the reaction of ReCl3(NO)2 with sodium fluoride in acetonitrile suspension in the presence of 15-crown-5. It forms green, slightly moisture sensitive crystals, which were characterized by IR spectroscopy as well as by an X-ray structure determination. Space group P21/c, Z = 4, 4821 observed unique reflexions, R = 0.040. Lattice dimensions at —60 °C: a = 1024.6(7), b = 801.4(4), c = 2386.6(12) pm; β = 99.90(4)°. The compound forms ion pairs via two Na—F contacts with bond lengths of 239.8 and 233.4 pm. Thus the sodium ion is seven-coordinate by the five oxygen atoms of the crown ether molecule and by two fluorine ligands of the [ReF2Cl2(NO)2]- unit. The nitrosyl groups of the anion are in transposition to the fluorine atoms and in cis-position to one another (symmetry C2v).
103Rh-NMR-Untersuchungen an Chloro-Bromo-Rhodaten(III) und Bestimmung der Stabilitätskonstanten im System [RhClnBr6-n]3-, n = 0-6 / 103Rh NMR Studies of Chloro-Bromo-Rhodates(III) and Determination of the Stability Constants in the System [RhCl„Br6-n]3-, n = 0-6
Authors: Kuhr W. , Peters G. , Preetz W.
Published: March 2015

By 103Rh NMR spectroscopy the ten compounds of the system [RhCl„Br6_„]3-, n = 0-6 are identified by separate signals. A downfield shift of approximately 160 ppm is observed per substitution of Cl by Br, and the stereoisomers for n = 2, 3, 4 are separated by at least 4 ppm. From the relative intensities of the 103Rh signals in equilibrated solutions, whose total contents of Rh. Cl and Br are known, six individual stability constants are calculated. Their product gives the overall stability constant, indicating [RhBr6]3- to be 36,300 times more stable than [RhCl6]3-. On treatment of [RhBr6]3- with HCl cis/fac isomers are formed stereospecifically, whereas the reaction of [RhCl6]3- with HBr gives trans isomers, n = 2 and 4, containing 20—30% of the cis compounds; only mer-[RhCl3Br3] 3- is obtained pure. The high resolution spectra of [RhCl6]3- and [RhBr6]3- are exhibit five signals each, reflecting the intensity patterns of the most abundant isotopomers within [Rh35Cln
37Cl6-n]3-, n = 2-6, and [Rh79Br„81Br6_„]3-, n = 1-5, respectively.
Notizen: 5-Deoxybostrycoidin, a New Metabolite Produced by the Fungus Nectria haematococca (Berk. and Br.) Wr.
Authors: Parisot Denise , Devys Michel , Barbier Michel
Published: March 2015

The structure 2 is established for 5-deoxybostrycoidin, a new metabolite isolated from cultures of the fungus Nectria haematococca (Berk. and Br.) Wr., on the basis of physico-chemical data (MS, 1H and 13C NMR, acetylation) and by reference to the known bostrycoidin 1.
Na10Ga6Sn3, eine Verbindung an der Zintl-Grenze / Na10Ga6Sn3, a Compound at the Zintl Border
Authors: Blase Wolfgang , Cordier Gerhard
Published: March 2015

The crystal structure of Na10Ga6Sn3 (a = 1457.6(3), c = 897.6(2) pm, P42/mnm, Z = 4) contains Ga12 icosahedra, which are connected by four of their eight exo-bound Sn atoms to form anionic chains 1
∞[Ga12Sn4Sn4/2]20-. The structure is discussed on the basis of the Zintl concept and Wade’s rules.
Preparation, Spectral Properties and Biological Activity of Cu(II), Zn(II) and Cd(II) Chelates of 8-Hydroxyquinoline-5-sulfonamides
Authors: Ibrahim S. A. , El-Gahami M. A. , Mahfouz R. M. , Farghali K. A.
Published: March 2015

The complexes of some quinolinol sulfonamides with Cu(II), Zn(II), and Cd(II) have been synthesized and formulated as [Cu(L)2(H2O)2] and [M(L)2]nH2O, M = Zn(II), or Cd(II), n = 0—3 and L = anion of the corresponding ligand. Their structures have been suggested by elemental analysis, electronic and IR spectroscopy, and conductivity measurements. It was found that the sulfonamide ligands are monobasic bidentate ON donors of the quinolinol group. Consequently, the Zn(II) and Cd(II) complexes are formulated as tetrahedral, whereas in Cu(II) complexes a distorted octahedral environment of the metal ion is proposed. It was proven that the metal chelates inhibit and actively affect the germination of wheat seed.
Isolation of Crystalline Potassium Alkanecarboselenoates
Authors: Kageyama Hideki , Takagi Kazutaka , Murai Toshiaki , Kato Shinzi
Published: March 2015

A series of potassium alkanecarboselenoates (2) were isolated as crystals from the reaction of the corresponding bis(acyl) selenides with potassium methanolate. The salts 2 readily react with alkyl iodides at 0°C to afford the corresponding alkyl alkanecarboselenoates (3) in quantitative yields.
Über Verbindungen subvalenter Hauptgruppenmetallkationen mit Dithiolaten, 4. Mitteilung [1] Die Kristallstrukturen der Verbindungen Pb[S(CN)C=C(CN)S] und (AsPh4)2{Pb[S(CN)C=C(CN)S]2} / Compounds of Subvalent Main Group Metal Cations with Dithiolates, Part 4 [1] Crystal Structures of Pb[S(CN)C=C(CN)S] and (AsPh4)2{Pb[S(CN)C=C(CN)S]2}
Authors: Hummel Hans-Ulrich , Meske Hermann
Published: March 2015

The crystal structures of Pb[S(CN)C=C(CN)S] and (AsPh4)2{Pb[S(CN)C=C(CN)S]2} have been determined by X-ray diffraction. PbS2C4N2, crystallizes in the non-centrosymmetric space group P21 with a = 7.292(3), b = 7.420(3), c = 5.789(2) Å, β = 95.47(5)° and Ζ = 2. The lead atom is coordinated by three S atoms of dithioligands. The coordination sphere around Pb includes a stereochemically active lone-pair and is described as a distorted tetrahedron. (AsPh4)2[Pb(S2C4N2)2] crystallizes in the triclinic space group P1 with a = 17.205(3), b = 13.342(3), c = 12.059(2) Å, α = 106.15(7), β = 102.92(6), γ = 79.50(3)° and Z = 2. In the complex anion {Pb[S(CN)C=C(CN)S]2}2- the Pb-atom is located at a centre of a distorted trigonal bipyramid with a stereochemically active lone-pair in an equatorial position.
Neuartige Dihydrazido- und Oxyamidoverbindungen der Phosphor- und der Thiophosphorsäure mit Bis(2-chlorethyl)amidosubstituenten / New Dihydrazido and Oxyamido Derivatives of Phosphoric and Thiophosphoric Acid with Bis(2-chloroethyl)amido Substituents
Authors: Giersdorf Konrad , Diefenbach Ursula , Engelhardt Udo
Published: March 2015

(Cl—CH2CH2)2N—P(=X)Cl2, X = O, reacts with 1,2-dimethylhydrazine in the presence of triethylamine to give the dihydrazide. Hexahydropyridazine as “cyclic hydrazine” leads to a tetracyclic side product formed by HCl elimination from the reactive 2-chloroethyl groups and active β-NH protons of the hexahydropyridazinyl substituents. The corresponding thio-compound, X = S. yields the monosubstitution product (Cl—CH2CH2)2N—P(=S)(N(CH3)—N(CH3)H)Cl. O-Benzylhydroxyamine hydrochloride substitutes both Cl-atoms at P to ioni (Cl—CH2CH2)2N—P(=S)(NH—O—CH2—C6H5)2. The corresponding phenylesters C6H5O—P(=X)(NH—O–CH2—C6H5)2, X = O, S, are prepared in a similar reaction.
Röntgenstrukturanalyse eines Diphosphaadamantans — ein erster Vertreter einer neuen Heterocyclenklasse / X-Ray Structural Analysis of a Diphosphaadamantane — First Derivative of a Novel Class of Heterocycles
Authors: Neidlein Richard , Funhoff Angelika S. , Krieger Claus
Published: March 2015

X-ray analysis of the intramolecular condensation product of methylene-bis-[bis-(2-oxopropyl)-phosphane oxide] (3) shows heteroadamantane structure. One of the C—P—C-angle seems to be very unusual. A value of only 95.5° was measured.
Die Kettenstrukturen der ternären Eisen(III)fluoride Rb2FeF5 und (CH3NH3)2FeF5 / The Chain Structures of the Ternary Iron(III) Fluorides Rb2FeF5 and (CH3NH3)2FeF5
Authors: Herdtweck Eberhard , Graulich Jens , Babel Dietrich
Published: March 2015

Single crystals of the orthorhombic compounds Rb,FeF5 (a = 756.5(1), b = 581.0(1), c = 1200.2(1) pm) and (CH3NH3)2FeF5 (a = 935.7(1), b = 789.6(1), c = 1017.2(1) pm) have been prepared and their structures determined by X-ray methods (wR = 0.025 and 0.029 for 983 and 954 reflections, resp.). Both compounds crystallize with Z = 4 in space group Pnma, but they form different chain structures: Rb2FeF5, isostructural with Rb,CrF5, exhibits cis-connected octahedra (bridging vs. average terminal Fe–F = 204.4/189.2 pm; Fe–F–Fe = 180°). In (CH3NH3)2FeF5, related to the (NH4),MnF5 structure type, the octahedra are trans-connected (Fe–F = 199.4/190.7 pm; Fe–F–Fe = 164.0°). These differences and the influence of hydrogen bonds (average N–H···F = 278.9 pm) in the methylammonium compound are discussed along with relations to further fluoride structures.
Notizen: Polysulfonylamine, XIX [1] / Kristallstruktur von (1-AcetyI-4-dimethylaminopyridinium)-dimesylamid bei –90 °C / Polysulfonylamines, XIX Crystal Structure of 1-Acetyl-4-dimethylaminopyridinium Dimesylamide at –90 °C
Authors: Jones Peter G. , Linoh Karin , Blaschette Armand
Published: March 2015

The crystal structure of the title compound was determined at —90 °C. It crystallizes in space group PĪ with a = 772.3(2), b = 1071.2(3), c = 1090.4(4) pm, α = 62.65(2), β = 82.71(2), γ = 71.42(2)° and Z = 2. The final R value was 0.031 for 2368 unique observed reflections. The presence of ion pairs in the solid state is observed, with short contacts of 290 pm between the pyridinium nitrogen and an oxygen of the anion. An analysis of the bond lengths suggests that the resonance form with a double bond to the nitrogen of the dimethylamino group and two localized double bonds in the ring, makes a larger contribution to the overall structure than in several similar pyridinium systems; the carbonyl moiety can however be regarded as containing a pure double bond.
Schwingungsspektren und Normalkoordinatenanalyse der Chloro-Bromo-Osmate(IV), [OsCl„Br6-n]2-, n = 0-6 / Vibrational Spectra and Normal Coordinate Analysis of Chloro-Bromo-Osmates(IV), [OsCl„Br6-n]2-, n = 0-6
Authors: Preetz W. , Irmer K.
Published: March 2015

The IR- and Raman spectra of the ten chloro-bromo-osmates(IV) [OsCl„Br6-n]2-, n = 0-6, including the geometrical isomers for n = 2, 3, 4 have been recorded at low temperature (80 K). The vibrational spectra of these complexes are completely assigned according to point groups Oh, D4h, C4v, C3v and C2v, supported by normal coordinate analyses based on a general valence force field. Due to the stronger trans-influence of Br as compared to Cl, in all asymmetric Cl—Os—Br axes the Os—Br bonds are strengthened and the Os—Cl bonds are weakened, indicated by valence force constants for Os— Br approximately 6% higher, for Os—Cl 6% lower, as compared with the values calculated for symmetrical Br—Os—Br and Cl-Os-Cl axes, respectively. The significantly stronger interaction between opposite bonds is revealed by the stretching interaction constants fdd, which are about three times larger than fdd for bonds at right angles.
Phosphinic and Phosphonic Acids I: Protonation and Complex Formation Equilibria of Some Substituted Ethane-1,1,2-tris-(P-methyl-phosphinie Acids)
Authors: Gaizer F. , Hägele G. , Goudetsidis S. , Papadopoulos H.
Published: March 2015

Protonation constants were determined pH-metrically for 3 selected phosphinic acids of the type CHRP*—CHP*2 (R = phenyl, methyl, t-butyl; P* = CH3P(O)OH). Complex formation equilibria were studied for metal ions Mg(II), Ca(II), Sr(II), Ba(II), Cu(II), Zn(II), Al(III) and Ga(III). Particular strong complex formation was observed for Ga(III).
Bicyclisch verbrückte Cyclopentadienylanionen: 4,8-Etheno-/Ethano-2,4,6,8-tetrahydro-s-indacen-dianion / Bicyclically Bridged Cyclopentadienyl Anions: 4,8-Etheno-/Ethano-2,4,6,8-tetrahydro-s-indacene Dianion
Authors: Atzkern Hermann , Köhler Frank H. , Müller Reinhard
Published: March 2015

Two cyclopentadienes have been linked in a stereochemically rigid arrangement such that the cyclopentadienes are not coplanar. The key intermediates in the synthesis were tetrakis(methylene)bicyclo[2.2.2]oct-2-ene (12) or -octane (14). The access to 12 and 14 was investigated in a comparative study including nine different precursors which were expected to lead to the methylene groups by elimination of HX. The best results were obtained with X = mesylate with overall yields of 52% for 12 in three steps and 42% for 14 in four steps. Other leaving groups facilitated the procedures, but more steps were required or the yield was lower. During these studies 21 tetrasubstituted bicyclo[2.2.2]oct-2-enes and -octanes were obtained and characterized, in particular by the δ(13C) and in most cases the 1J(13C –1H) and δ(1H) values. Both 12 and 14 added CBr2 selectively in that only isomers with two dibromo-(vinyl)cyclopropane fragments per molecule were obtained. One isomer showing C2-symmetry could be isolated from the mixture. After reaction with methyllithium the corresponding linked cyclopentadienes with unsaturated (20) or saturated bridge (21) were obtained and fully characterized. Metallation of 20 and 21 gave the title dianions in quantitative yield.
Raman- und 27Al-NMR-Untersuchungen über die Existenz des Heptachlorodialuminat-Ions [Al2Cl7]- in den festen Reaktionsprodukten der Zusammensetzung MCl · 2 AlCl3 (M = K, Rb, Cs) / Raman and 27Al NMR Investigations on the Existence of the Heptachlorodialuminate Ion [Al2Cl7]- in the Solid Reaction Products of the Composition MCl · 2 AlCl3 (M = K, Rb, Cs)
Authors: Reich Peter , Müller Dirk , Feist Michael , Blumenthal Gert
Published: March 2015

The Raman and 27Al NMR spectra of the title substances have been investigated with special regard to the earlier postulated [Al2Cl7]- ion. The Raman spectra represent a superposition of the spectrum of the [AlCl4]- ion as well as of AlCl3 (s). Likewise the 27Al NMR spectra indicate AlCl species with coordination number 4 and 6 of Al. It is concluded that the postulated [Al2Cl7]- ion with an Al–Cl–Al bridge does not exist in the compounds investigated. The literature concerning [Al2Cl7]- is critically reviewed.
Synthesis of Some New Pyrrolo Heterocycles of Pharmaceutical Interest from 1,4-Diphenylpyrrolidine-2,3,5-trione+
Authors: Metwally Mohamed Abbas , Sofan M. A.
Published: March 2015

Continuing earlier studies designed to obtain derivatives of pharmacological interest, some novel compounds 2, 5, 6, 7 and 8 were prepared using 1,4-diphenylpyrrolidine-2,3,5-trione (1) and 1,2-phenylenediamines, o-aminophenol, 1,3-diphenylacetone and thiosemicarbazide, respectively. The hydrazino derivative (8) was obtained from 7 and hydrazine hydrate. Structural identification was obtained by 1H NMR, mass spectra and IR spectral data.
Chemistry of Alkylheterocyclic Aromatic π-Deficient Compounds: A Novel Synthesis of Cinnolines
Authors: Elnagdi Mohamed Hilmy , Maksoud Abdul-Aal Fatma Abdul , Taha Nadia M. , Yassin Youssef Mahfouz
Published: March 2015

A novel synthesis of cinnolines by reacting arylidenemalononitrile derivatives with 1-aryl-1,6-dihydro-6-oxo-pyridazin-3,5-dicarbonitriles is reported.
Notizen. Metallkomplexe mit biologisch wichtigen Liganden, LIV . Palladium(II)- und Kupfer(II)-Komplexe von 2-Polyhydroxyalkyl-4-thiazolidincarbonsäure (Monosaccharid-Cystein-Verbindungen) / Metal Complexes of Biologically Important Ligands, LIV. Palladium(II) and Copper(II) Complexes of 2-Polyhydroxyalkyl-4-thiazolidine Carboxylic Acid (Monosaccharide Cysteine Compounds)
Authors: Chen Jingtang , Pill Thomas , Beck Wolfgang
Published: March 2015

The title ligands, derived from monosaccharides and cysteine, form bis(chelate) complexes of palladium(II) and copper(II). According to their IR spectra the ligands are N,Ο-coordinated to copper(II), whereas N,S and O,S coordination to palladium(II) is observed.
Substitutionsreaktionen am Niobtetrafluorid-Komplex (η5-C5Me5)NbF4 / Substitution Reactions on the Tetrafluoro Niobium Complex (η5-C5Me5)NbF4
Authors: Xu Yuming , Roesky Herbert W. , Schrumpf Frank , Noltemeyer Mathias
Published: March 2015

Cp*NbF4 (1) (Cp* = η5-C5Me5) reacts with lithium salts of β-diketones under elimination of LiF to form the chelate complexes

(2) and

(3). The X-ray crystal structure of 3 was investigated and is compared with the homologous tantalum compound.
Darstellung und Struktur des Selenamid-Komplexes SeCl2[N =PPh2N = S(O)Me2I2 / Synthesis and Structure of the Seleniumamid Complex SeCl2[N = PPh2N = S(O)Me2]2
Authors: Schrumpf Frank , Roesky Herbert W. , Noltemeyer Mathias
Published: March 2015

The reaction of two equivalents of Me3Si—N=PPh2N=S(O)Me2 (1) with SeOCl2 proceeds with elimination of (Me3Si)2O to yield SeCl2[N=PPh2N=S(O)Me2]2 (2) as a white powder. Crystals of 2 that are suitable for X-ray crystal structure analysis have been obtained by recrystallization from acetonitrile. The structure of 2 shows very short selenium-nitrogen bonds.
Umsetzungen von Ferrocenyl-lithium mit Carbonyleisen-Komplexen / Reactions of Ferrocenyl Lithium with Carbonyliron Complexes
Authors: Herberhold Max , Feger Wolfgang , Thewalt Ulf
Published: March 2015

The reaction of cis-Fe(CO)4Br, with ferrocenyl lithium, FcLi, leads to the binucleara hexacarbonyldiiron complexes Fe2,(CO)6(μ-Br)(μ-CFc) (7), Fe,(CO)6(μ-COFc)2 (8) and Fe2(CO)6(μ-C2Fc2O) (9)b. Addition of FcLi to Fe(CO)5 gives the ferrocenoyl tetracarbonylferrate anion which was characterized as the salt NEt4
+[Fe(CO)4(FcCO)]- (10); 9 is obtained after reaction of the anion with Meerwein’s salt, Me3O+BF4
-.

The reaction of Fe2(CO)9 with FcLi, followed by methylation with Me3O+BF4
-, results in the formation of Fe2(CO)8[μ2-C(OMe)Fc] (11) which can be extracted from the product mixture using pentane. Chromatography of the product mixture over silica, however, leads preferentially to the formation of trinucleara complexes of the type Fe3(CO)9(μ3-COMe)(μ3-CR) (R = Fc (12), OMe (13) and O(CH2)4OMe (14)) in addition to 9; the same products are obtained starting from Fe3(CO)12. No complexes could be isolated which contained a direct iron σ-ferrocenyl bond. The structures of the new complexes were deduced from their infrared, mass, 1H and 13C NMR spectra. The bis(ferrocenoyl)-bridged compound 8 was also characterized by an X-ray crystallographic structure analysis.
Cyclotriphosphazen-2-spiro-3′-cyclodiphosphadiazan und Cyclotriphosphazen-2-spiro-3′-cyclodiphosphadiazan-6′-spiro-2″-cyclotriphosphazen – Spiroverbindungen aus Cyclotriphosphazen und Cyclodiphosphadiazanen / Cyclotriphosphazene-2-spiro-3′-cyclodiphosphadiazane, Cyclotriphosphazene-2-spiro-3′-cyclodiphosphadiazane-6′-spiro-2″-cyclotriphosphazene – Spiro Compounds from Cyclotriphosphazene and Cyclodiphosphadiazanes
Authors: Engelhardt Udo , Diefenbach Ursula , Damerius Reinhard
Published: March 2015

Hexachlorocyclotriphosphazene (Cl2P=N)3 reacts with hydrazine or dihydrazidophosphoric acid O-phenyl-ester in THF in the presence of triethylamine to give the spirocyclic title compounds. Constitutions are confirmed by MS, NMR and IR spectra. {1H}31P NMR spectra at 36.23 MHz are of higher order – ABCD and A2BB′A′2 – and can be simulated with the appropriate shifts and coupling constants.
Darstellung und Kristallstruktur von Nd2SeSiO4 / Preparation and Crystal Structure of Nd2SeSiO4
Authors: Grupe M. , Urland W.
Published: March 2015

Nd2SeSiO4 has been prepared as violet rod-like single crystals by reaction of elemental neodymium, selenium and iodine in the ratio 1.0:1.0:2.5 and subsequent reaction with quartz glass powder. The compound crystallizes in the orthorhombic space group Pbcm with a = 618.2(2), b = 717.4(2), c = 1102.4(2) pm and Z = 4. The structure is built up of alternating NdSe- and NdSiO4-sheets.
The Crystal Structure of Me3SiNPPh2CH2PPh2 and NMR Investigations on its Proposed Thermal Isomerization
Authors: Schmidbaur Hubert , Bowmaker Graham A. , Kumberger Otto , Müller Gerhard , Wolfsberger Werner
Published: March 2015

The crystal structure of Me3SiNPPh2CH2PPh2 (1) has been determined in order to obtain information about the ground state conformation in the solid, and about unusual steric effects which could give rise to conformational isomers. It was recently proposed that such isomers exist due to restricted rotation about the P=N bond, and are generated by heating the compound to 160 C. The evidence for them was based on the observation of multiple NMR signals in CDCl3 solutions of samples which had been so treated. The crystal structure yields a P–N–Si bond angle of 150.2(2), a P–N bond length of 1.529(3) Å and a Si–N bond lengths of 1.668(3) A. It is clear that, as a result of the relatively large P–N–Si angle in 1, there is no steric hindrance to rotation about the P–N bond in this molecule. Attempts to study the energetics of the proposed isomerization by recording the NMR spectra of heated samples showed that the previously reported multiple NMR signals are not generated in this way. However, such signals are generated at ambient temperature under various circumstances, for example in the course of the reaction of a CDCl3 solution of 1 with methanol to produce HNPPh2CH2PPh2 (2). The observation that it is not necessary to heat 1 in order to generate these signals makes their assignment to rotational isomers rather less likely. In the absence of a reproducible method of producing these signals in a pure sample, the existence of such isomers should be regarded as not yet proven.
Dithioquadratato-Komplexe von Kupfer(II) und Kupfer(I). / Dithiosquarate Complexes of Copper(II) and Copper(I).
Authors: Krause Ralf , Mattes Rainer
Published: March 2015

From aqueous solutions of potassium dithiosquarate and bis(ethylenediamino)copper(II) sulfate the following compounds have been obtained: [CuII(en)2][CuII(C4O2S2)2] (2) and [CuII(en)2(H2O)]2[Cu4
I(C4O2S2)4] · 2 H2O (3). Their structures have been determined: Crystal data, 2, monoclinic, space group C 2/c, a = 1914.5(6), b = 823.0(1), c = 1669.5(5) pm, β = 133.23(1)°, Ζ = 4; 1809 reflections, R = 0.024. 3, triclinic, a = 779.2(3), b = 958.7(4), c = 1478.8(4) pm, α = 82.34(3), β = 82.68(2), γ = 73.47(3)°, Ζ = 1; 3376 reflections, R = 0.045. 2 contains infinite chains of centrosymmetrical [Cu(en)2]2+ cations and bisphenoidal [Cu(C4O2S2)2]2- anions. 2 shows ferromagnetic behaviour above 75 K. At lower temperatures antiferromagnetic coupling between the chains dominates. 3 contains isolated [Co(en)2H2O]2+ cations and tetrameric [Cu(C4O2S2)]- anions. The anion consists of a chain of tetrahedrally and trigonally coordinated Cu(I) atoms with short Cu · · · Cu distances of 255.2( 1 ) and 257.9( 1 ) pm. The dithiosquarate ligands are stacked in pairs.
Kommentar zur Synthese und Kristallstruktur von 1,1-Dichlor-3,5-diphenyl-4H1,2,4,6- λ 4-selenatriazin, SeCl2C2N3H(C6H5)2 / Comment on the Synthesis and Crystal Structure of 1,1-Dichloro-3,5-diphenyl-4H1,2,4,6-λ4-selenatriazine, SeCl2C2N3H(C6H5)2
Authors: Dehnicke Kurt
Published: March 2015

1,1-Dichloro-3,5-diphenyl-4 H-1,2,4,6-λ4-selenatriazine
Darstellung und Struktur von (CH3NH3)3PrCl6 · 2 H2O / Synthesis and Structure of (CH3NH3)3PrCl6 · 2 H2O
Authors: Runge Petra , Schulze Mathias , Urland Werner
Published: March 2015

(CH3NH3)3PrCl6 · 2 H2O has been prepared as light green, air sensitive crystals by the reaction of PrCl3·xH2O with [CH3NH3]Cl in ethanol. The compound was characterized by crystal structure determination. Crystal data: monoclinic space group I 2/a, Z = 8. Lattice constants: a = 1963.3(4), b = 925.9(3), c = 1954.3(4) pm, β = 90.56(1)°. The compound forms [PrCl4(H2O)2]--chains where two Pr3+-ions are connected via two chlorine atoms. The magnetic behaviour of (CH3NH3)3PrCl6· 2H2O has been studied.
Das Metallcarbonyl OsCo2(CO)11: Verbesserte Darstellung und einige Reaktionen / The Metal Carbonyl OsCo2(CO)11: Improved Synthesis and Some Reactions
Authors: Tasi Miklos , Bernhardt Wolfgang , Vahrenkamp Heinrich
Published: March 2015

Of several methods tested to improve the yield of the metal carbonyl OsCo2(CO)11 (1), the reaction of H2Os(CO)4 with Co2(CO)6μ-C2H2) was found to give the best results (>50%). The availability of 1 allowed to study its capping reactions with C2H4S, PhPH2 and alkynes RC≡CH leading to the products OsCo2(CO)9(μ3-X) for X = S (2), PPh (3), and RC=CH (4). The capped clusters are thermally more stable than the corresponding RuCo2(CO)9 derivatives, and the alkyne capped species are more difficult to transform to the vinylidene capped clusters OsCo2(CO)9(μ3-C=CHR) (5) than the analogous RuCo2 species.
Syntheses and Electrochemical Properties of [C5Me5Ru]+ Complexes with Polycyclic Arenes. Crystal Structure of[(C5Me5)Ru( μ6-chrysene)]PF6 · 0.5 Me2CO
Authors: Chavez Ivonne , Cisternas Andrés , Otero, Margarita , Román Enrique , Müller Ulrich
Published: March 2015

Mononuclear and binuclear compounds [(C5Me5)Ru(η6-arene)PF6 and [(C5Me5Ru)2(η6,η6-arene)](PF6)2 were prepared by reacting (C5Me5)RuCl2, the arene and silver acetate with subsequent addition of NH4PF6, for arene = phenanthrene, chrysene, triphenylene, fluorene, bifluorene, biphenyl and 4,4′-biphenyl. The mononuclear compounds were also prepared for arene = naphthalene, anthracene, pyrene and coronene. The 1H and 13C NMR spectra are reported. By cyclic voltammetry all compounds show a first reduction potential that is considerably more positive compared with the free arene. The first cathodic wave is irreversible for a wide range of scanning speeds. However, the mononuclear coronene and the binuclear phenanthrene compounds show reversibility. The crystal structure of [(C5Me5)Ru(η6-chrysene)]PF6·0.5 Me2CO was determined by X-ray diffraction (3797 unique observed reflexions, R = 0.098). Crystal data: a = 1689.2(2), b = 1524.0(8), c = 2263.5(3) pm, β= 107.22(1)°, space group P21/n, Ζ = 8. Crystallographically independent, two cations [(C5Me5)Ru(η6-chrysene)]+ and two anions PF6
- are present, but their structures are essentially equal. The [C5Me5Ru]+ unit is bonded to one of the terminal benzene rings of the chrysene in a sandwich manner; the rings bonded to Ru are nearly coplanar. The PF6
- ions and the C5Me5 rings exhibit strong thermal vibrations.
Gemischtvalente Telluridhalogenide des Aluminiums, Galliums und Indiums: Verbindungen E3Te3Hal auf Gehaltsschnitten ETe — ETeHal / Mixed Valency Tellurohalides of Aluminium, Gallium and Indium: Compounds E3Te3Hal on Pseudobinary Sections ETe — ETeHal
Authors: Paashaus Sabine , Kniep Rüdiger
Published: March 2015

The pseudobinary systems ETe — ETeHal (E/Hal = Al/I, Br; Ga/I, Br, Cl; In/I, Br) contain the intermediate phases E3Te3Hal, having incongruent melting behavior (decomposition at temperatures between 386 °C and 718 °C). The crystal structures (orthorhombic, Pnma) of the isotypic ternary phases contain one-dimensional macromolecules, in which (Te3/3EIIIHal)-tetrahedra and (Te3/3Ga2
IITe3/3) units (staggered conformation) are linked by common Te—Teedges. The macromolecules can be described in terms of fragments of an ETe-crystal structure of the GaTe structural type. In this way, halogen acts as an oxidizing agent which then saturates the free valence at the EIII positions. Larger fragments of a respective ETe-crystal structure are expected to be present in the crystal structure of InTeCl (x ≈ 0.16) which is an intermediate phase (m. p. = 418 °C; incongruent) in the quasibinary system InTe — InTeCl.
Notizen: Experimental Evidence for 1,2-Fluorine Atom Migration in Tritiated 1,1,2-Trifluoroethyl Radical
Authors: Kotaka Masahiro , Kohida Tomoyuki , Sato Shin
Published: March 2015

Tritiated compounds containing 2,2,2-trifluoroethyl groups were formed by the reaction of tritium atoms with trifluoroethylene. The result can be accepted as definitive evidence for a 1,2-fluorine atom migration occurring in the reaction intermediate, tritiated 1,1,2-trifluoroethyl radical.
Notizen: Investigations on Less Volatile Hay Blossom Constituents
Authors: Jirovetz Leopold , Buchbauer G. , Nikiforov A. , Remberg G. , Raverdino V.
Published: March 2015

Five samples (headspace, steam distillation, Likens-Nickerson, methanolic and dichloromethane extracts) of Austrian hay blossoms have been investigated by chromatographic-spectroscopic methods and led to the identification of several non or less volatile compounds (mainly in the Likens-Nickerson extract).
Ferrocen-1,1′-dithiolato- und -diselenato-Derivate des Hexachlor-cyclotriphosphazens / Ferrocene-1,1′-dithiolato and -diselenato Derivatives of Hexachloro-cyclotriphosphazene
Authors: Herberhold Max , Dörnhöfer Christine , Thewalt Ulf
Published: March 2015

The three pairs of geminal chloro substituents in hexachloro-cyclotriphosphazene, N3P3Cl6, are stepwise replaced by chelating ferrocene-1,1′-dichalcogenato groups, [Fe(C5H4E)2.]2-, to give the spiro-cyclotriphosphazenes N3P3Cl6-2n[(EC5H4)2Fe]n (n = 1, 2, 3; E = S (a), Se (b)). The molecular structure of P,P′-bis(ferrocene-1,1′-dithiolato)-P″-dichlorocyclotriphosphazene, N3P3Cl,[(SC5H4)2Fe]2(2a) has been determined.
A Monomeric Methanedithiolate Complex of Molybdenum
Authors: Okuda Jun
Published: March 2015

Thermal reaction of moiybdenocene dihydride (η5-C5H5)2MoH2 with carbon disulfide affords a new molybdenocene complex (η5-C5H5)2Mo(S2CH2) which according to analytical and spectroscopic data contains a methanedithiolate ligand.
Ferrocenyl-aryl-plumbane / Ferrocenyl-aryl-plumbanes
Authors: Utri Gerhard , Schwarzhans Karl-Eberhard , Allmaier Günter M.
Published: March 2015

The first example of a diplumba[1.1]ferrocenophane[cpPb(ø2)cp]2Fe2 has been prepared from ø2PbCl2 and 1,1′-dilithioferrocene 2 TMEDA. The preparation of further four ferrocenyl-phenyl-plumbanes, including the hitherto unknown compounds (ø3Pbcp)2Fe, Fc2Pb2ø2 and [(ø3Pb)cpFecp]FcPbø2 has been achieved by reaction of a mixture of monolithioferrocene · TMEDA and 1,1′-dilithioferrocene 2 TMEDA with ø 2PbCl2 and ø3PbCl, respectively.

These compounds have been investigated by 1H, 13C and 207Pb NMR spectroscopy as well as by half-wave potential measurements, EI, FD and PD mass spectrometry.

The results were discussed in terms of the possibility of Pb/Fe metal orbital overlap.

There is evidence from the VT 1H NMR spectra for conformational flexibility of the diplumba[ 1.1 ]ferrocenophane.
Metal Complexes of Biologically Important Ligands, LV Binding of Steroidal Hormones through α-Amino Acid Ligands to Platinum(II) and Palladium(II)
Authors: Ehrenstorfer-Schäfers Eva-Maria , Steiner Norbert , Altman Janina , Beck Wolfgang
Published: March 2015

3-(2-Aminoethoxy)estrone, 3-(2-aminoethoxy)estradiol, 17 α-aminomethylestradiol and 3-ol-17-aminoestrane react with coordinated activated amino acid ligands of platinum(II) and palladium(II) complexes to give cis- and trans-Cl2Pt(GlyNHR)2, Cl2Pt[(Gly)„NHR]2 and Cl2Pd(HisNHR) (R = steroid, n = 1-3). Similarly estrone, prednisolone, prednisone and testosterone have been bound in α-amino acid ester complexes cis-Cl2Pt(GlyOR)GlyOH, trans-Cl2Pt(GlyOR)2 and Cl2Pd(HisOR) (R = steroid).
β-Acylvinyl-dicarbonyl-η5-cyclopentadienyl-eisen-Komplexe / β-Acylvinyl-dicarbonyl-η5-cyclopentadienyl-iron Complexes
Authors: Gompper Rudolf , Kottmair Eduard
Published: March 2015

Reactions of β-chlorovinylcarbonyl compounds 10, 14, 16, 18, 20, 22, with sodium dicarbonyl-η5-cyclopentadienyl-ferrate (NaFp) furnish β-acylvinyl-dicarbonyl-η5-cyclopentadienyliron complexes 15, 17, 19, 21, 23 and binuclear iron complexes 26-29. Spectral data demonstrate the donor effect of the Fp group. Irradiation of these complexes in the presence of triphenylphosphane delivers β-acylvinyl-carbonyl-η5-cyclopentadienyl-triphenylphosphane-iron complexes 34, 35. Reaction of glutarimides with oxalyl chloride gives rise to oxazolo-[3,2 a]pyridines 13. Benzylidenemalonyl chloride reacts with FpCS2Na to form benzylidenethietane-2,4-dione (32). A β-acylethinyl-carbonyl-η5-dicyclopentadienyl-iron complex 43 has been prepared.
The Influence of High Concentrations of Fluoride on the Electrosynthesis of Peroxodisulfates at β-PbO2 Anodes
Authors: Scheler Irene , Wabner Dietrich W.
Published: March 2015

During electrolysis with β-PbO2 anodes in acidic sulfate electrolytes high current efficiencies of peroxodisulfate are obtained (60-70%) when high amounts of fluoride (1 Mol · 1-1 to 3 Mol · 1-1) are added to the electrolyte. This reaction is examined by means of current efficiency of peroxodisulfate, rate of ozone formation, polarization curves, and impedance measurements. The reason for the high current efficiencies is the formation of fluorosulfonic acid in the electrolyte and its reaction with the OH-radical (from the discharge of H2O) to form HSO4-radicals.
[η2-Bis(di-t-butylphosphino)methan](trans-stilben)nickel(0), Ni(dtbpm)(trans-PhCH = CHPh). Synthese und Molekülstruktur einer Vorstufe des 14-Elektronenfragments [Ni(dtbpm)] / [η2-Bis(di-t-butylphosphino)methane](trans-stilbene)nickel(0), Ni(dtbpm)(trans-PhCH=CHPh). Synthesis and Molecular Structure of a Precursor for the 14-Electron Fragment [Ni(dtbpm)]
Authors: Hofmann Peter , Perez-Moya Luis A. , Krause Martin E. , Kumberger Otto , Müller Gerhard
Published: March 2015

The synthesis of [η2-bis(di-t-butylphosphino)methane](trans-stilbene)nickel(0), Ni(dtbpm)(trans-PhCH=CHPh) (17), is reported. This novel, stable Ni(0)-olefin complex can be prepared from dichloro[η2-bis(di-t-butylphosphino)methane]nickel(II), Ni(dtbpm)Cl2 (18), which is easily accessible from anhydrous NiCl2 and bis(di-t-butylphosphino)methane, (dtbpm, 12). Lithium-powder reduction of 18 in the presence of an excess of trans-stilbene in ether at low temperature yields 17. For both 17 and 18 X-ray structure determinations have been carried out and the results for the olefin complex 17 are reported and discussed in detail. 17 is the first bisphosphane Ni(0) olefin complex in which the d10 metal is part of a four-mem-bered bisphosphane chelate ring with an accordingly very small P—Ni—P angle (79.6°). The molecular geometry of 17 reveals electronic structure characteristics, bonding capabilities and steric properties for the Ni(dtbpm)-unit, which are in accord with previous theoretical predictions. 17 can serve as a convenient precursor to generate the strongly bent d10-ML2 14-electron fragment [Ni(dtbpm)] (13) in solution. This reactive intermediate can be trapped, yielding various derivatives of the stereoelectronically anomalous Ni(0) fragment 13.
Silaheterocyclen, VII. Reaktionen des Dichlorneopentylsilaethens mit Aldehyden / Silaheterocycles, VII. Reactions of Dichloroneopentylsilene with Aldehydes
Authors: Auner Norbert , Seidenschwarz Claudia
Published: March 2015

Dichloroneopentylsilene, Cl2Si=CHCH2Bu' (1), is produced from vinyltrichlorosilane (2) and LiBu' in n-pentane at —78 °C. The reactions of 1 with aromatic aldehydes like benzaldehyde and the 4-methoxy- or 4-fluoro-substituted derivatives, naphthalene-1- and -2- and 9-anthracenecarbaldehyde, furfurale and its S-analogous thiophene carbaldehyde yield 1,2-silaoxetanes by [2+2] cycloaddition with the carbonyl group. The same is true for the reactions of 1 with pivaline-, butyr- and acetaldehyde. The silaoxetanes cannot be isolated; the formation of dichlorovinylsiloxanes and the olefinic compounds R—CH=CH —CH2Bu′suggests that the cycloreversion of the Si—O four-membered ring competes with an intramolecular isomerization, evidently via formation of a zwitterionic intermediate

. The product formation by coupling reactions of lithiated aldehydes and 2 is excluded by performing analogous reactions with the chlorosilanes Me2SiCl(R) (R = Cl, Me, Vi).
Tetraphenylphosphonium-hexachloroarsenat, PPh4[AsCl6]; Synthese und Kristallstruktur / Tetraphenylphosphonium Hexachloroarsenate, PPh4[AsCl6]; Synthesis and Crystal Structure
Authors: Bebendorf Joachim , Müller Ulrich
Published: March 2015

When ozone is passed through a solution of (PPh4)2[As2Cl8] in dichloromethane at –40 °C, first an instable red compound forms, then intense yellow PPh4[AsCl6] is obtained. The latter can also be obtained by introducing chlorine instead of ozone. The crystal structure of PPh4[AsCl6] was determined by X-ray diffraction (844 observed unique reflexions, R = 5,9%). Crystal data: tetragonal, space group P4/n, a = 1305.6(3), c = 752.2(4) pm, Z = 2. The structure is isotypic with that for other PPh4[MCl6] compounds, the octahedral AsCl6
- ions being situated on fourfold rotation axes and showing a well-known positional disorder in that they are somewhat tilted against the symmetry axes due to packing strain.
Synthesis and Crystal Structure of Ordered, Orthorhombic α-NbBr5
Authors: Hönle Wolfgang , Furuseth Sigrid , Schnering Hans Georg von
Published: March 2015

Niobium pentabromide, NbBr5, is prepared in the orthorhombic ordered (α)-form from the elements in sealed quartz ampoules (Nb powder, Br2, l) at 973 K. The structure has been determined from single crystal data (a = 1288.8(2), b = 1869.0(3), c = 614.9(1) pm; Pnma (No. 62); Z = 8; R = 0.055). α-NbBr5_ forms dimeric Nb2Br10 molecules with d̄(Nb–Brb) = 271.5 pm, d̄(Nb–Bre) = 240.8 pm and d̄(Nb– Bra) = 246.1 pm. α-NbBr5 is a diamagnetic semiconductor with cgsχmol
dia(300 K) = –72 × 10-6 cm3/mol. The band gaps of NbCl5, α-NbBr5 and NbI5 have been determined by diffuse reflection to be Eg(NbCl5) = 2.74 eV, Eg(α-NbBr5) = 1.99 eV, and Eg(NbI5) = 0.99 eV.
Solutions of Gallium Trichloride in Ethers: A 71Ga NMR Study and the X-Ray Structure of GaCl3 · Monoglyme
Authors: Böck Stefan , Nöth Heinrich , Wietelmann Astrid
Published: March 2015

Solutions of GaCl3 in various ethers have been studied by 71Ga NMR spectroscopy. σ71Ga data indicate that the predominant species in diethylether and tetrahydrofuran solutions are GaCl3 · O(C2H5)2 and GaCl3. 2OC4H8, respectively. However, in monoglyme solution dissociation occurs and the product crystallizing from the solution is [cis-GaCl2(monoglyme)2]GaCl4 as demonstrated by an X-ray structure determination of the solvate GaCl3 · monoglyme.
Struktur und magnetische Eigenschaften von [CuII(2-thiooxamat)2] · 1,6H2O / Structure and Magnetic Properties of [CuII(2-thiooxamat)2] · 1,6 H2O
Authors: Krause Ralf , Mattes Rainer
Published: March 2015

The reaction of CuSO4·5 H2O with potassium 2-thiooxamate, K[NH2C(S)CO2], yields [Cu(2-thiooxamate)2]·1.6 H2O. Crystal data: a = 1501.6(8), b = 1650(1), c = 375.4(2) pm, β = 90.65(5)°, Ζ = 4. The structure was refined with 2213 reflections to R = 0.044. Copper(II) is chelated by two thiooxamate ligands, which act as O- and S-donors forming five-membered chelate rings. This cis-planar [Cu(2-thiooxamate)2] molecules are stacked. The axial coordination sites at copper(II) interact within the stacks with O- and S-donor atoms of neighbouring units. Above 60 K the magnetic susceptibility follows the Curie-Weiss law with antiferromagnetic coupling.
79,81Br and 133Cs Nuclei Quadrupole Interactions and Phase Transitions in Crystalline Caesium Perbromate
Authors: Tarasov V. P. , Privalov V. I. , Buslaev Yu. A. , Eichhoff U.
Published: March 2015

NMR experiments in solid caesium perbromate have recently been performed at magnetic fields of 1.88 T and 7.04 T together with spectral simulations for 79Br, 81Br and 133Cs in solid caesium perbromate. The line shapes are dominated by quadrupole effects. For bromine the quadrupole asymmetry parameter [η] is observed to be zero at all temperatures while the quadrupole coupling constant (CQ) as a function of temperature shows two approximately linear regions on either side of a non-linear region between 200 K and 260 K where an extended orientational phase transition occurs. 133Cs shows an increase of CQ and a decrease of η with increasing temperature. This behaviour may be associated with an anisotropic change of the “a” lattice parameter.
Die Bindungsverhältnisse in Phosphantelluriden. Eine empirische NMR-Studie und die Kristallstruktur von (iso-C3H7)3PTe [1] / The Nature of the Bonding in Phosphane Tellurides. An Empirical NMR Study and the Crystal Structure of (iso-C3H7)3PTe [1]
Authors: Kuhn Norbert , Henkel Gerald , Schumann Hans , Fröhlich Roland
Published: March 2015

31P and 125Te NMR data of trialkylphosphane tellurides are compared. The deviation of the shifts for Me3PTe and 'Bu3PTe from those of other phosphane tellurides is interpreted in terms of high s-character of the P–Te bond originating from the phosphorus (R = Me) and the tellurium (R = 'Bu) atom, respectively. The molecular structure of 'Pr3PTe has been determined by X-ray crystallography (P–Te 2.365 A). A reduction of the bond order is suggested based also on a comparison of the R3PSe and R3PTe NMR data.
Notizen: Variety of Oxidation States of Manganese Ions in Compounds with Tripod-Like Tetradentate Ligands
Authors: Nishida Yuzo , Nasu Miyuki , Tokii Tadashi
Published: March 2015

From the reaction mixture of Mn(III) acetate and several tripod-like ligands, a Mn(II) complex, a binuclear Mn(III) complex with (μ-oxo)(μ-acetato) core, and a Mn(III)–Mn(IV) complex with a di-μ-oxo bridge were obtained. This demonstrates that the oxidation state of the manganese ion in these compounds is drastically affected by small changes in ligand character.