bluuebunny/crossref_metadata_2025 huggingface dataset:
Kristallisationsvorgänge bei melallreichen Rubidiumoxiden / Crystallisation Processes in Metal Rich Rubidium Oxides
Authors: Deiseroth H. J. , Simon A.
Published: February 2015

On the basis of X-ray investigations a structural model for the orientational disorder of Rb9O2 clusters in the rubidium suboxide Rb6O is derived, which is in accordance with details of the thermal analysis of the ordering process.

In the second part the thermal and structural investigations of a metastable phase of the probable composition Rb6,33O are described. The phase is formed by warming quenched samples RbxO (9 >x > 7) to co. 140 K and decomposes at ca. 183 K. Its cubic structure bears relationships to the structure of rubidium as well as to YB66 (replacing B12 icosahedra in the latter compound by Rb atoms).

A special DTA instrument used for the investigation of Rb6,33O is described.
Die Kristall-und Molekülstrukturen zweier trans-Diaza-diphosphetidine / Crystal and Molecular Structures of Two trans-Diazadiphosphetidines
Authors: Schwarz Wolfgang , Hess Heinz , Zeiss Werner
Published: February 2015

The crystal structures of (MeOPNPh)2 and [Me(Me2N)2P2N2(SiMe3)2] I were determined. Both compounds proved to be four-membered rings with a trans-configuration of the electronegative groups. The first compound crystallizes in the monoclinic space group P21/c with a = 876.3 pm, b = 944.8 pm, c = 941.4 pm, β = 99.69°, Z = 2, the second compound in the orthorhombic space group P212121 with a = 879.5 pm, b = 985.7 pm, c = 2594.6 pm and Z = 4. The final R-values are 0.064 and 0.043, respectively.
Montanin-C, A New Furanoid Diterpene from Teucrium montanum L
Authors: Malakov Peter Y. , Papanov Georgi Y. , Mollov Nikola M. , Spassov Stefan L.
Published: February 2015

A new furanoid diterpene of clerodane type, Montanin-C (1) is isolated from the bitter fraction of the arial parts of Teucrium montanum L., spread in Bulgaria. Its structure is established on the basis of spectral evidance and chemical transformations.
Untersuchung von isomeren Tripeptiden und Derivaten des Thyrotropin-,Releasing" Hormons durch Elektronenstoß- und Felddesorptions-Massenspektrometrie / Investigation of Isomeric Tripeptides and Thyrotropin-Releasing Hormone Derivatives by Electron Impact and Field Desorption Mass Spectrometry
Authors: Lüderwald I. , Przybylski M. , Ringsdorf H. , Silberhorn D. , Kaibacher H. , Voelter W.
Published: February 2015

The complementary informations from field desorption and electron impact mass spectra of free tripeptides and thyrotropine releasing hormone derivatives can be used to determine primary structure and molecular weight. Characteristic and diagnostic fragmentation pathways, the formation of diketopiperazines and the temperature-dependent tendency to form amine fragments and diketopiperazines will be discussed.
Crystal and Molecular Structure of a New Linear Chain Compound: Bis(diphenylglyoximato)platinum(III)perchlorate
Authors: Endres H. , Keller H. J. , Sand H. van de , Dong Vu
Published: February 2015

The reaction of bis(diphenylglyoximato)platinum(IV) diiodide with AgClO4 in benzene yields red brown needles of the compound bis(diphenylglyoximato)platinum(III) perchlorate (A) and crystals of bis(diphenylglyoximato)platinum(III) perchlorate which contains additionally between one and one and a half moles of benzene per formula unit (B). Both compounds are highly hygroscopic and instantaneously change their color to black-green in a humid atmosphere. Crystals of A are tetragonal, a = 20.325(2), c - 6.519(4) Å, space group D8
4h-P4/ncc, Z = 4. The structure consists of stacks of [Pt(dpg)2]+ cations with equidistant Pt-Pt separations of 3.259(4) Å. The Perchlorate ions are disordered in channels formed by the cation columns. Crystals of B are triclinic, a = 14.29(3), b = 13.54(2), c -10.34(3) Å, a = 85.2(2), β = 113.2(2), γ = 93.9(2)°.
Groups Übergangsmetall-substituierte VB-Elementsysteme, 12 [1] Ein- und zweikernige Übergangsmetallkomplexe mit Dihalogenarseneinheiten / Transition Metal Substituted VB Element Systems, 12 [1] Mono-and Dinuclear Transition Metal Complexes with Dihalogenarsenic
Authors: Malisch Wolfgang , Panster Peter , Alsmann Robert
Published: February 2015

The reaction of ASCl3 with the transition metal anions [η5-C5H5(CO)3M]⊖ (M = Cr, Mo, W) yields the arsenic transition metal complexes η5-C5H5(CO)3M-AsCl2, which readily form trans-η5-C5H5(CO)2LM-AsCl2 in the presence of phosphorus donors [L = P(OCH3)3, P(CH3)2C6H5].

Addition of M(CO)5-groups on the trivalent arsenic occurs with THF · M′(CO)5 (M′ = Cr, Mo) leading to the arsenic bridged dinuclear complexes η5-C5H5(CO)3Cr-AsCl2-M′(CO)5. Controlled Cl/F-exchange at the bridged species can be achieved by use of AgBF4.
Komplexchemie reaktiver organischer Verbindungen, XXV [1] Stabilisierung von Diphenylmethylen und Diphenyldiazomethan in Carbonylcobalt-Komplexen / Complex Chemistry of Reactive Organic Compounds, XXV [1] Stabilization of Diphenylmethylene and Diphenyldiazomethane in Carbonyl Cobalt Complexes
Authors: Herrmann Wolfgang A. , Schweizer Ilona
Published: February 2015

Low temperature photolysis of (η5-C5H5)Co(CO)2 with diphenyldiazomethane in tetrahydrofurane yields μ-carbonyl-μ-diphenylmethylene-bis(η5cyclopentadienylcobalt) (Co-Co) and μ3-earbonyl-μ3-(diphenylmethylenehydrazido)(N.N.N)-cyclotris(η5-cyclo-pentadienylcobalt) (3 Co-Co). The bridged μ-diphenylmethylene complex is also formed by thermal reaction of (η5-C5H5)Co(CO)2 with diphenyldiazomethane in boiling benzene.
Ein Beitrag zur Zusammensetzung des Insektizides "Toxaphen®" Gaschromatographisch-massenspektroskopische Charakterisierung eines öligen und eines kristallinen Anteils des technischen Toxaphens und dessen insektizide Wirksamkeit / A Contribution to the Composition of the Insecticide "Toxaphene®" Gaschromatographic-Masspectroscopical Characterisation of the Oily and the Crystalline Fraction of Technical Toxaphene and their Insecticidal Activity
Authors: Parlar H. , Nitz S. , Michna A. , Körte F.
Published: February 2015

Technical Toxaphene can be separated in two fractions by recrystallisation which are investigated with the help of GC/MS and toxicological methods. Especially the Retro-Diels-Alder-fragmentations give specific informations on the structure of highly chlorinated bornane derivatives representing the main components of the technical mixture. For this study lower chlorinated bornanes are used as model substances. Toxicological investigations show that both fractions have lower activity than technical toxaphene.
Novel Rearrangement of 5-Arylazo-2-thiohydantoin Derivatives with Alkali and Aromatic Amines
Authors: Shalaby A. F. A. , Daboun H. A. , Abdel Aziz M. A.
Published: February 2015

5-Arylazo-2-thiohydantoin derivatives (2a,c) were cleaved and rearranged by aqueous sodium hydroxide to give the corresponding 1-aryl-⊿2-1,2,4-trazole-5-imino-3-carboxylic acids (3a-c). 3 a was decarboxylated to 1-phenyl-⊿2 -1,2,4-triazoline-5-imine (5). Hydrolysis of 5-arylazo-1-phenyl-2-thiohydantoins (6a-c) behaved in different manner affording 1-aryl-4-phenyl-⊿2 -1,2,4-triazoline-5-thione-3-carboxylic acids (7a-c). Fusing (2a-c) with aromatic amines at high temperature gave the corresponding anilides (8a-h). Treatment of 5-arylidene-2-thiohydantoin derivatives (9a-c) with hydrazine hydrate gave colourless products of thioureido cinnamic acid hydrazide derivatives (10a-c), while refluxing 5-arylidene-2-methylmercaptohydantoin (11a-d) with hydrazine hydrate and/or benzo-phenone hydrazone gave the corresponding glycocyamidine derivatives (12a-g).
Synthesis of Xanthone-O-glycosides, I Synthesis of 3-0-β-Glycosides
Authors: Chari V. M. , Klapfenberger R. , Wagner H.
Published: February 2015

The synthesis of hydroxy-xanthone-3-O-β-glycosides by condensation of the appropriate aglycone and the acetyl-α-D-glycosyl bromide in pyridine solution in presence of silver carbonate is described. The naturally occurring l-hydroxy-3-O-β-primeverosyl-7-methoxy xanthone (gentioside) has been synthesized and its structure thereby confirmed.
Strontiumchromat(V, VI), Sr2,67⃞0,33(CrO4)1,33(CrO4)0,67, eine Hochtemperaturphase mit Defekt-Bariumphosphat-Struktur / Strontiumchromate(V, VI), Sr2,67⃞0,33(CrO4)1,33(CrO4)0,67, a High- Temperature Compound with Defect-Bariumphosphate Structure
Authors: Hartl K. , Braungart R.
Published: February 2015

Black hexagonal platelets growing on strontiumoxide in the presence of chromium (III)-oxide and air at temperatures from 1250 to 1400 °C have been shown to belong to the rhombohedral space group R3̅m. In hexagonal orientation the elementary cell has the axes a0 = 1115.8 ± 0.9 pm and c0 = 4037 ± 3,6 pm and Z = 24, Dx=4.26. Structurally the compound is closely related to Ba3(PO4)2, with the exception, that there are defects in the metal sub-lattice. At temperatures below 1200 °C Strontiumchromate(V, VI) decomposes into the dis-crete chromates(V) and -(VI). At temperatures from 113 to 338 K the compound is an electronic semiconductor with an activation energy of 0.26 eV.
Derivatives of eis-NPCl2(NSOCl)2 and (NPCl2)2NSOCl, Part IX [1] Substitution Reactions of cis-NPCl2(NSOCl)2 with Piperidine
Authors: Baalmann H. H. , Keizer R. , Grampel J. C. van de , Kruk C.
Published: February 2015

Aminolysis of cis-NPCl2(NSOCl)2 by piperidine in acetonitrile at room temperature proceeds via a non-geminal substitution pattern. During the first substitution step the reactivity of a SOCl-centre appears to be greater than that of a PCl2-centre. The second and third substitution step successively take place at the PCl2- and remaining SOCl-centre. The different isomeric forms of the mono-, bis-, tris-, and tetrakis(piperidino) derivatives are characterized by means of 31P NMR data. Application of 13C NMR leads in two cases to a structure assignment.
Molekül-und Elektronenstruktur des Thioheteroanions [S2 WS2CoS2WS2]2- / Molecular and Electronic Structure of the Thiohetero Anion [S2WS2CoS2WS2]2-
Authors: Müller A. , Mohan N. , Bögge H.
Published: February 2015

The crystal and molecular structure of [(C6H5)4P]2[Co(WS4)2] was determined from single crystal X-ray diffraction data (space group P21/c with a = 18.542(4), b = 15.443(2), c= 18.713(2) Å, β= 108.73(1)°, Z = 4). In the complex anion Co is coordinated by two bidentate chelating WS4
2- anions, with a nearly tetrahedral surrounding of Co. The bond lengths in the planar metal sulfur ring CoS2W are Co-S = 2.26 Å and W-S = 2.22 Å, while the terminal W-S bonds are 2.14 Å.
Synthesen mit aliphatischen Dialdehyden, XXVII [1] Eine „non-template“-Synthese zur Darstellung metallfreier 1.4.8.11-Tetraaza [14] annulen-Derivate / Syntheses with Aliphatic Dialdehydes, XXVII [1] A Non-Template Synthesis for the Preparation of Metal-Free 1,4,8,11-Tetraaza[14]annulene Derivatives
Authors: Reichardt Christian , Scheibelein Wolfgang
Published: February 2015

The reaction of 2-substituted malonaldehydes (7) with aromatic 1,2-diamines (5 or 6) in ethanol/acetic acid (10:1) leads to 6,13-disubstituted 1,4,8,11 -tetraaza[14]annulene derivatives (8 or 9) even in the absence of coordinating metal cations ("non-template" synthesis), and not to 3-substituted 1,5-benzodiazepines such as 4. Cobalt(II), nickel(II), and copper(II) complexes of the macrocyclic chelate ligands 8 and 9 have been observed by subsequent metallization with the corresponding acetates in N,N-dimethylformamide. The structures of 8-11 have been assigned mainly by their mass spectra.
Über 2.2′-Biphenylylenphosphorsäuren und die gaschromatographische Trennung von Lewis-Basen an Bis(2.2′-biphenylylendithiophosphato) nickel(II) / On 2.2′-Biphenylylenephosphorie Acids and the Gas Chromatographie Separation of Lewis-Bases on Bis(2,2′-biphenylylenedithiophosphato )niekel (II)
Authors: Kuchen Wilhelm , Mahler Hans F.
Published: February 2015

Dibenzo(d,f )-1,3,2-dioxaphosphorepines, 2,2′ -Biphenylylenephosphoric Acids, Bis (2,2′ -biphenylylenedithiophosphato) - nickel (II), Gas Chromatography
Photoelectron Spectra of Dithiapropellanes
Authors: Kobayashi Michio , Gleiter Rolf
Published: February 2015

The photoelectron spectra of the dithiapropel-lanes 1 to 5 have been recorded. The first bands have been assigned by comparison with the PE spectra of cyclic thioethers. The resonance inte-gral between the 3p orbitals of the sulfur centers in 1 to 5 is found to be -0.15 to -0.25 eV.
Die Kristallstruktur von Bis(eyclopentadienyl)mangan, eine polymere Verbindung mit Cyclopentadienyl-Brücken /The Crystal Structure of Bis(cyclopentadienyl)manganese, a Polymerie Compound with Cyclopentadienyl Bridges
Authors: Bünder Wolfgang , Weiss Erwin
Published: February 2015

The dark brown anti-ferromagnetic modification of (C5H5)2Mn crystallizes ortho-rhombic, space group Pna21 (or Pnam) with a= 1402.7(2), 6 = 582.9(1), c = 996.5(1) pm and Z = 4. It forms polymer chains with a zigzag arrangement of C5H5Mn units and additional bridging C5H5-rings between adjacent ions. The normals to the planes of the C5H5-bridges form an angle of 25° to the Mn-Mn-axes. All Mn-C bond distances are longer than expected for covalent bonds, suggesting essentially ionic bonding in agreement with the magnetic behaviour of (C5H5)2Mn. The observed antiferromagnetism is attributed to interactions between the manganese ions via the C5H5-bridges.
Darstellung und Eigenschaften von und Reaktionen mit metallhaltigen Heterocyclen, I Metallorganische Komplexe von Mangan und Rhenium mit zwei funktionellen Zentren /Preparation and Properties of and Reactions with Organometallic Heterocycles, I Organometallic Complexes of Manganese and Rhenium with two Functional Centres
Authors: Lindner Ekkehard , Au Günter von , Eberle Hans-Jürgen
Published: February 2015

The binuclear anions Na2[(OC)4MP(O)R2]2 (2a, a′, b, b′) [M = Mn: R = CH3 (a), C6H5 (a′); M = Re: R = CH3 (b), C6H5 (b′)] can be obtained quantitatively by reduction of the phosphinic acid complexes (OC)4BrMP(OH)R2 (1a, a′, b, b′) with sodium amalgam in ether. While the manganate anions 2 a, a′ can be transformed with excess sodium into the mononuclear salts Na2[(OC)4MnP(O)R2] (3a, a′), with two nucleophilic centres, the corresponding anions 2 b, b′ eliminate CO to give sparingly soluble species. From 3 a, a′ and dimethylsulphate the doubly methylated compounds CH3Mn(CO)4P(OCH3)R2 (4a, a′) are obtained. The rhenium derivatives CH3Re(CO)4P(OCH3)R2 (4b, b′) are formed only in very poor yields from 2 b, b′ and dimethylsulphate under reductive conditions. The IR, 1H NMR, and mass spectra are discussed.
Synthese und chemischer Transport ternärer Verbindungen, untersucht am Beispiel CoO + Nb2O5 = CoNb2O6 /Synthesis and Chemical Transport of Ternary Compounds, Investigated with CoO + Nb2O5 = CoNb2O6
Authors: Schäfer Harald , Trenkel Marita
Published: February 2015

Chemical transport reactions (1273 → 1073 K) with CoO, Nb2O5 or CoNb2O6 using TeCl4 as transport agent have been made. The experimental results are compared with thermodynamic calculations. General rules for the treatment of chemical transport calculations concerning ternary compounds are given.
Vier-und fünfgliedrige Phosphorheterocyclen, XXXIV Cycloaddukte aus Phosphazenen der Koordinationszahl 2, 3 und 4 /Four-and Five-Membered Phosphorus Heterocycles, XXXIV Cycloadducts from Phosphazenes of Coordination Number 2, 3, and 4
Authors: Schmidpeter Alfred , Criegern Thomas von
Published: February 2015

Dimethyl azaphosphole (la) and aminoiminophosphine (2) give the first example of a [2 + 2]-Cycloaddition of a2- and c^-phosphazenes. The resulting diazadiphosphetidine (4) dissociates reversibly. For the corresponding cycloadduct from l a and the aminodiiminophosphine (3) a rapid exchange of the exocyclic imino group and the ring nitrogen via a zwitterionic form is observed.
Photochemical Reductive trans-Elimination from trans-Diacidotetracyanoplatinate(IV) Complexes
Authors: Vogler A. , Kern A. , Fußeder B. , Hüttermann J.
Published: February 2015

Upon CT excitation the complex ions trans-[Pt(CN)4N3X]2- and trans-[Pt(CN)4X2]2- (X = Cl and Br) undergo a reductive trans-elimination with formation of [Pt(CN)4]2- and two ligand radicals in the photoprimary step. The formation of a Pt(III) intermediate is not observed. Due to the stability of [Pt(CN)4]2-, recombination reactions regenerating the starting complex are efficient if the ligand radicals are not scavenged. For the azide complexes the high quantum yields for the production of [Pt(CN)4]2- are explained by the instability of azide radicals. For trans-[Pt(CN)4X2]2-, the recombination is efficient in aqueous solution, while in ethanol the halogen atoms are scavenged by hydrogen abstraction. The sequence of steps following CT excitation can be explained by a potential energy diagram.
Halogeno-und Pseudohalogeno-tris(pentahaptocyclopentadienyl)uran(IV)- Komplexe als Lewis-Säuren: Darstellung und Struktur trigonal-bipyramidaler Uran-Organyle des Typs [(η5 -C5H5)3UXL] / Tris(pentahaptocyclopentadienyl)uranium(IV) Halides and Pseudohalides as Lewis-Acids: Preparation and Structure of Uranium Organyls [(η5 -C5H5)3UXL] with Trigonal-Bipyramidal Coordination
Authors: Fischer R. D. , Klähne E. , Kopf J.
Published: February 2015

The first two examples of a novel series of organo-actinide complexes, [Cp3UXL] (Cp = η5 -C5H5, X = halide or pseudohalide anion, L = uncharged Lewis base), are described. The X-ray structure analysis of the system with X = NCS and L = CH3CN confirms an almost linear alignment (H3)CCNUNCS along with the coplanarity of the three Cp ring normals. The remarkable Lewis acidity of certain Cp3UX-compounds appears to be essential for the formation of oligomeric species [Cp3UX]∞ as well as for specific reactions of monomeric CP3UX.
Bifunktionelle Acyl(diorganyl)phosphane und ihr Verhalten gegenüber molekularem Sauerstoff / Bifunctional Acyl(diorganyl)phosphanes and their Behavior Towards Molecular Oxygen
Authors: Lindner Ekkehard , Vordermaier Gottfried
Published: February 2015

The bifunctional acylphosphanes RC(O)P(Ph)-(CH2)2-(Ph)PC(O)R (1 a-c) [R = CH3 (a), CF3 (b), C5H6 (c)] are obtained from [NaP(Ph)CH2-]2 and the corresponding acid chlorides RC(O)Cl. Etherical solutions of 1 a-c with molecular oxygen easily can be transformed into the dioxides [RC(O)P(O)(Ph)CH2-]2 (2a-c). In contrast to the monofunctional acyl(diaryl)phosphane oxides 2 a-c do not react with water at 25 °C. The 31P, 19F, 1H NMR and IR spectra of the new compounds 1, 2 a-c are discussed.
Verbindungsbildung im System Ag2S-GeS2-AgI / Compound Formation in the System Ag2S-GeS2-AgI
Authors: Nagel Alois , Range Klaus-Jürgen
Published: February 2015

Besides the well-known argyrodite (Ag8GeS6), the new compound Ag2GeS3 could be synthesized from Ag2S-GeS2 mixtures. Ag2GeS3 crystallizes in an orthorhombic variant of the Wurtzite structure. Treatment of Ag2GeS3 in a AgI/AgCl-eutectic yields the quaternary compound Ag7GeS5I. Crystal data for Ag7GeS5I and some analogous compounds are given.
Synthesis of 5,6-Diaryl-1,2,4-triazines
Authors: Soliman Farid S. G. , Labouta Ibrahim M. , El Sebai A. Ibrahim , El Dine S. A. Shams
Published: February 2015

The synthesis of 6-(4-methoxyphenyl)-5-phenyl-3-oxo-2,3-dihydro-1,2,4-triazine (5a) from 4-methoxybenzoin, 4-methoxybenzil, or 4-methoxybenzoin semicarbazone and semi-carbazide hydrochloride is reported. The condensation of 4-methoxybenzil with thiosemi-carbazide yielded 6-(4-methoxyphenyl)-5-phenyl-3-thioxo-2,3-dihydro-I,2,4-triazine (5b) which was converted to its 3-oxo analogue 5 a with acetic anhydride. Reduction of 5 a and 5 b with zinc and aqueous acetic acid led to the corresponding 2,3,4,5-tetrahydro-1,2,4-triazines 6 a and 6b, respectively. Oxidation of 5 b with iodine in sodium carbonate solution afforded bis [6-(4-methoxyphenyl)-5-phenyl-1,2,4-triazin-3-yl]disulphide (7). Analogous triazines were prepared by condensing 3,3'-diiodobenzil with semicarbazide hydrochloride or thiosemicarbazide.
Carbenium Periodide, I / Carbenium Periodides, I
Authors: Lecea M. J. Volz-de
Published: February 2015

Carbocations of the tri-phenylmethylseries give with In - salts which are characterized by the natur of the anion. The preparation and general physical, spectral and chemical properties of tris-(4-dimethylaminophenyl)-carbenium-triiodid (1), a salt of crystal violet, and bis-(4-dimethylaminophenyl)-phenyl-carbenium-triiodid (2), a salt of malachite green, are described. The structure of the cations and anions of these carbeniumsalts is determined from their spectral data.
Zur Reaktivität von C=N-Doppelbindungssystemen, XVI [1]. Eine Synthese von 2-Hydroxy-6-oxo-1.6-dihydro-pyridinen / The Reactivity of C=N Double Bond Systems, XVI [1]. Synthesis of 2-Hydroxy-6-oxo-1,6-dihydro-pyridines
Authors: Ziegler Erich , Wipfler Helmut , Knierzinger Andreas , Wolfbeis O. S.
Published: February 2015

The combined action of triethyl orthoformate and aniline upon Meldrum's acid or 5-aza-5-phenyl-1-oxaspiro[5,5]undecan-2,4-diones gives their anilinomethylene derivatives (2, 5), which react with methyleneactive nitriles in dimethylformamide to give substituted 2-hydroxy-6-oxo-1,6-dihydro-pyridines (7) in excellent yields.
Tri(tert-butyl)phosphinoxid, -imin, -methylen und -boran / Tri(tert-butyl)phosphine Oxide, Imine, Methylene and Borane
Authors: Schmidbaur Hubert , Blaschke Günter
Published: February 2015

Tri(tert-butyl)phosphine Oxide, Imine, Methylene, Borane Tri(tert-butyl)phosphine oxide, imine, methylene and borane have been prepared and their properties investigated. The imine is chemically inert due to strong steric hindrance. Its thermal decomposition at 200 °C leads to tri(tert-butyl)-pliosphine, in contrast to the methylene analogue which undergoes reductive elimination of isobutene. Both the oxide and borane are thermally very stable (> 250 °C).
Austauschreaktionen an komplexgebundenen Liganden von Elementen der V. Hauptgruppe, VI [1]. Lithiierung von η5-C5H5Mn(CO)2PH3 / Exchange Reactions at Complexed Ligands of Elements of Group Vb, VI [1]. Lithiation of η5-C5H5Mn(CO)2PH3
Authors: Höfler Mathias , Hausmann Heinz , Schneider Annegret
Published: February 2015

The metallation of η5 -C5H5Mn(CO)2PH3 with excess n-butyllithium and consecutive reactions with CH3I and (CH3)3SiCl yield the complexes η5 -C5H5Mn(CO)2PR3 (R = CH3, Si(CH3)3). The product of the lithiation is proposed to be η5-C5H5Mn(CO)2PLi3.
Über eine neue Modifikation von As2O5/On a New Modification of As2O5
Authors: Jansen Martin
Published: February 2015

High temperature Guinier photographs of As2O5 indicate a continuous phase transition to HT-As2O5, which is accomplished at 305 ± 3 °C. The crystal structure of HT-As2O5 has been derived from the low temperature form; space group and lattice constants are P41212-D4
4 and a = 857.2 pm, c = 463.6pm (310 °C), respectively. According to symmetry considerations, the phase transition is expected to be of pure ferroelastic-paraelastic type (422F 222).
Kinetics and Mechanism of Oxidation of Thiocyanate Ion by Sodium N-Chloro-4-methyl Benzene Sulphonamide in Alkaline Medium
Authors: Mahadevappa D. S. , Gowda B. T. , Gowda N. M. M.
Published: February 2015

Kinetics of oxidation of potassium thiocyanate by the oxidant chloramine-T (CAT) in presence of NaOH has been studied at 30 °C. At low substrate concentrations, the approximate rate law is, - d[CAT]/dt = k[CAT][KNCS]/[NaOH]2 . At higher substrate concentrations, the rate law simplifies to, -d[CAT]/dt = k[CAT]/[NaOH]. Ionic strength and addition of p-toluene sulphonamide have negligible influence on the rate. The rate of reaction decreases in D2O medium and the value of the inverse solvent isotope effect, kH2O/kD2O is 0.46. The reaction has been studied at different temperatures and the activation parameters have been calculated.
The Alkyl Inductive Effect. I. Relations between σI*, σ* and ρI ρ* for H and Alkyl Groups; σI Values from the Size and Branching of R
Authors: Levitt Leonard S.
Published: February 2015

For alkyl groups it is shown that new inductive substituent constants, σI (R), can be calculated accurately from previously obtained polar substituent constants, σ*(R), from the simple relation σI(R) = σI (Me) [I-2σ* (R)]. In similar fashion, the two reaction constants are related by ρI/ρ* = σ* (H)/σI (Me) = 10.6. Many new σI values are presented for groups for which no previous estimate has been available. The attentuation of σI (R) with alkyl size for n-alkyl groups is shown to be a function of the number of C atoms, nc: σI(R) = -0.137 nc/(2nc + 1). The effect of branching of R is also discussed.
Friedel-Crafts -Alkylierungen mit Cu2+ -Bentonit/Friedel -Crafts -Alkylations with Cu2+ -Bentonite
Authors: Lotz W. W. , Gosseick J.
Published: February 2015

It is shown that Cu2+ -bentonite produces high yields of mono-t-butyl-benzene in Friedel-Crafts-alkylation. The ratio of mono-and di-product is investigated in dependence of the content of water in the bentonite: dry Cu2+ -bentonite produces high yields of mono-product, moistered Cu2+ -bentonite leads to di-alkylated products.
Crystal and Molecular Structure of Bis(N,N,N′,N′ -tetramethyl-1,4-diaminobenzeniumyl) [Wurster s Blue Cation]-tetracyanoplatinate(II)-mono-hydrate
Authors: Endres H. , Jentsch W. , Keller H. J. , Martin R. , Moroni W. , Nöthe D.
Published: February 2015

The title compound crystallizes in the monoclinic space group A 2/m (C2h
3) with a = 10.61(3) Å, b = 9.511(5) Å and c = 16.47(5) Å, β = 124.2(1)° and two formula units in the unit cell. The structure was solved by Patterson and Fourier methods and refined by least squares to R = 0.071 based on 1251 observed intensities. The organic cations are slightly distorted and are arranged in dimers along the crystallographic a-axis. There are “mixed stacks” of the planar [Pt(CN)4]2− units which are separated from each other by the WB2
2+ dimers along b. There is IR-evidence for the formation of hydrogen bridges between [Pt(CN)4]2− units and the crystal water during the modification change of the compound at room temperature.
Struktur und Schwingungsspektren von Monomolybdaten und Monowolframaten organischer Kationen / Structure and Vibrational Spectra of Monomolybdates and Monotungstates with Organic Cations
Authors: Thiele Axel , Fuchs Joachim
Published: February 2015

The crystal structures of dicyclohexylammonium-monomolybdate dihydrate [(C6H11)2NH2]2MoO4 · 2 H2O, (I), cyclohexylammonium-monomolybdate, (C6H11NH3)2MoO4, (II) and tert-butylammonium-monotungstate, (C4H9NH3)2WO4, (III), were elucidated. In I the anion has nearly tetrahedral structure, in II one Mo-O distance is significantly shorter than the other three, and in III all four W-O distances are different. In spite of the variety of structures the following basic principles are recognizable: 1) Each hydrogen atom of the cationic amino groups as well as of the water of crystallization forms hydrogen bridges. 2) Never are oxygen atoms of the same MoO4 connected by these bridges, but always oxygen atoms of neighbouring MoO4 units. 3) From an oxygen atom emanate either two or no hydrogen bridge. For the investigated molybdates (tungstates) there are in all instances isomorphous tungstates (molybdates). The number and position of the vibrational bands is in good agreement with the observed anion symmetry Td, C3v and C1, respectively.
Synthesen und Reaktionen von 4-Bora-2.6-diphospha-1.3.5-triazenen Cyclische Borbetaine / Synthesis and Reactions of 4-Bora-2,6-diphospha-1,3,5-triazenes Cyclic Boron Betaines
Authors: Binder Herbert , Palmtag Jürgen
Published: February 2015

By substitution of chlorine in the title compound 2,2,4,4,6,6-hexachloro-3,5-dimethyl-4-bora-2,6-diphospha-1,3,5-triazene (1) new members of this class of compounds are synthesized. In most cases reaction starts first on the boron site. The ring reactivity can be accounted for in terms of the charge distribution in the heterocycle 1. In 1 the coupling 2 J(31 P-N-11 B) could be detected for the first time. A mechanism for the ring formation is discussed.
Phosphinsubstituierte Carbonyl-Seleno-Komplexe des Mangans und Rheniums Phosphine / Substituted Carbonyl Seleno Complexes of Manganese and Rhenium
Authors: Küllmer Volker , Röttinger Erika , Vahrenkamp Heinrich
Published: February 2015

The selenium bridged complexes [(CO)4M-SeX]2 (M = Mn, Re; X = H, SnMe3) were converted by trimethylphosphine to the dimers [Me3P(CO)3M-SeX]2 and/or the monomers (Me3P)2(CO)3M-SeX. The obtained Se-SnMe3 compounds reacted with HCl to form the SeH compounds. The structures of the new complexes were deduced from their IR and NMR spectra. [(Me3P)2(CO)3Re]2Se, the first monobridged bis-carbonylmetal chalcogenide, was obtained as a byproduct and confirmed by a crystal structure analysis.
13C-und 119Sn-NMR-Spektren von Thienylstannanen / 13 C and 119 Sn NMR Spectra of Thienylstannanes
Authors: Wrackmeyer Bernd
Published: February 2015

The assignment of some 13 C chemical shifts in 2-thienylstannanes has to be reversed. Proton coupled 119 Sn NMR spectra are shown to be useful to detect long range Sn-H coupling, not readily obtained from complex 1H NMR spectra.
Ternäre Chalkogenide M3M2′X2 mit Shandit-Struktur / Ternary Chalcogenides M3M2′X2 with Shandite-Type Structure
Authors: Zabel Manfred , Wandinger Sigrid , Range Klaus-Jürgen
Published: February 2015

Metal-rich ternary chalcogenides M3M2′X2 (M = Ni, Co, Pd, Rh; M′ = In, Tl, Pb, Sn; X = S, Se) with Shandite-type structure were synthesized from mixtures of the elements and/or binary components. A single-crystal investigation on Co3ln2S2 verifies the rhombohedral unit cell of Shandite-type compounds, originally postulated by Peacock and McAndrew (Crystal data for Co3ln2S2: Rhombohedral, space group R3̄m; a = 549,31 (6) pm, a = 57.89°, Z= 1; 3 Co in 3d, 1 In(l) in 1 a, 1 In(2) in 1 b, 2 S in 2c with x = 0.2790).
Cis-trans-Isomere von Diazadiphosphetidin-Derivaten: Fünf Kristall- und Molekülstrukturen / Cis-trans Isomers of Diazadiphosphetidine Derivatives: Five Crystal and Molecular Structures
Authors: Pohl Siegfried
Published: February 2015

The crystal structures of the compounds [R3CP(X)NR]2(R= CH3; X=S, Te for cis isomers and X= lone pair, S, Te for trans isomers) (2-6) were determined from single crystal X-ray data. The four-membered P-N rings in the cis isomers 2 and 3 show significant deviations from planarity attributed to steric overcrowding in the molecules.The trans isomers 4-6 are planar. The P-N bond lenghts (mean values for 2-6:171.4, 170, 171.6, 169.2 and 168.3 pm)in the cis isomers are not significantly different from the corresponding lengths in the trans isomers 5 and 6.
Reactions with Cyclic Amidenes III: Synthesis of Some New Fused Pyrazole Derivatives
Authors: Elnagdi Mohamed Hilmy , Kandeel Ezzat Mohamed , Sadek Kamal Usef
Published: February 2015

Diazotised 5-amino-3-hydroxy-4-phenylazopyrazole (1 a) and 3,5-diamino-4-phenylazo-pyrazole(1 b) coupled with active methylene reagents to yield the pyrazolo[1,5-c]-as-triazine derivatives (3a, b-5 a, b). On the other hand coupling of diazotised 1 a, with β-naphthal has afforded the acyclic azo derivative(6).

Whereas diazotised 1 a underwent intramolecular cyclisation into the pyrazolo[1,5-c]-1,2,3,4-tetrazine derivative (3)on attemptet addition to acrylonitrile, diazotised 1 b reacted with acrylonitrile under the same conditions to yield the pyrazolo[1,5-c]-pyridazine derivative (4).

Compounds 1 a, b reacted with benzoylisothiocyanate to yield the pyrazol-5-ylthiourea derivatives (10 a, b). Where as 10 a readily cyclised into the pyrazolo[3,4-c]-as-triazine derivative (11) on refluxing with pyridine, compound 10 b hydrolysed under the same conditions into the pyrazol-5-ylthiourea derivative (12).
Keto-enol Tautomerism in 4,7-Dioxo-4,5,6,7- tetrahydroindoles
Authors: Malesani Giorgio , Quintily Ugo , Chiarelotto Gianfranco
Published: February 2015

The tautomeric equilibria of 4,7-dioxo-4,5,6,7-tetrahydroindoles have been investigated by nuclear magnetic resonance spectroscopy. Proton chemical shift measurements have been made for a series of alkyl or arylindole derivatives, and equilibrium constants ([enol]/[keto]) have been determined. The effect of solvent on the enol-keto equilibria has been studied.
Darstellung und Struktur von NaAlSi und NaAlGe / Preparation and Structure of NaAlSi and NaAlGe
Authors: Westerhaus Wolfgang , Schuster Hans-Uwe
Published: February 2015

The intermetallic compounds NaAlSi and NaAlGe have been prepared and their structure has been determined by powder data. They crystallize in an anti-PbFCl-type lattice with the following cell dimensions:

NaAlSi:

a = 413.5 pm, c = 737.9 pm, c/a = 1.785;

NaAlGe:

a = 416.4 pm, c = 742.7 pm, c/a = 1.784.
Notizen: Konkurrenzreaktionen einiger tricyclischer Diene zur [2+2]PhotocycIoaddition / Competitive Reaction of Some Tricyclic Dienes to [2+2]Photocycloaddition
Authors: Parlar H.
Published: February 2015

The UV-behaviour of some chlorinated tri-cyclic dienes (1 a-e) was studied in acetone. Cycloaddition (2 a-b and 2 d-e), hydrogen-transfer (3 c′ and 3 d) and photo ene-(3 c)-reaction products could be isolated and identified with the help of spectroscopic methods.
Notizen: Quinolyl-nitro Ethylenes and Nitrostyryl-quinolines of Molluscicidal Activity
Authors: Kamel M. M. , Korkor M. I. , Shoeb H. A. , Tammam G. H. , El - Amin S.
Published: February 2015

For possible molluscicidal activity, 1-(4- quinolyl)-2-nitro ethylenes, 1-(4-quinolyl)-2- methyl-2-nitro ethylenes, 2-styryl, and 2- (p-nitro styryl)-quinolines were synthesized.
Notizen: Reaktionen von Malonsäurediamid mit SbCl5 / The Reaction of Malonamide with Antimony(V)chloride
Authors: Dietrich W. , Latscha H. P.
Published: February 2015

Malonamide reacts with antimony(V)chlorid to a 1:2-adduct (1) at roomtemperature. By heating this complex dichloromalonamide (2) was formed; hydrolysis of the complex yields a new heterocycle with the composition C3H4Cl5N2O2Sb (3).
Über eine neue Präparationstechnik in der Feststoffchemie, II Hochdruck-Hochtemperatursynthesen mit CO2 -Laser / A New Preparative Technique in Solid State Chemistry, II High Pressure -High Temperature Reactions with CO2-Lasers
Authors: Müller-Buschbaum Hk. , Pausch H.
Published: February 2015

A new technique to realize solid state reactions under high oxygen pressure is reported. This method is based on the use of CO2-Laser radiation in combination with autoclave technique. The experimental set-up is described.
Zur Synthese phosphinkomplexierter d8-Metalltetrasulfide (Ni(II), Pd(II) und Pt(II)) mit Natriumpolysulfiden / On the Synthesis of Phosphine-Coordinated d8-Metal Tetrasulfides (Ni(II), Pd(II), and Pt(II)) with Sodium Polysulfides
Authors: Schmidt Max , Hoffmann Gerhard G.
Published: February 2015

A short literature survey on phosphine-coordinated d8-metal tetrasulfides is given. Different results have been reported for the reactions of elemental sulfur with Pt(PPh3)4 (1). The reaction of sodium polysulfides, Na2Sx, with the corresponding dihalides results in a clear-cut manner in the formation of the already known compounds tetrasulfidoethylenebis(diphenylphosphine)palladium(II) (6) and tetrasulfido-bis(triphenylphosphine)-platinum(II) (5), and the new compound tetrasulfido-ethylenebis(diphenylphosphine)-nickel(II) (13). Degradation reactions of [Pt(S5)3]2-(9) with triphenylphosphine, tri-p-tolylphosphine and ethylene-bis(diphenylphospbine) result in the formation of 5, and tetrasulfido-ethylenebis(diphenylphosphine)platinum(II) (4) and the new tetrasulfidobis( tri-p-tolylphosphine)platinum(II) (10). IR-spectra are reported.
Das Verhalten von Mono- und Diorganylphosphansulfiden gegenüber Metallcarbonylsystemen, XXI [1]Darstellung und Eigenschaften von Di[μ-{(dicarbonyl-h5-cyclopentadienylmangan) dimethylphosphin}thio]-bis- (tetracarbonylrhenium), (OC)4Re[h5-C5H5Mn(CO)2P(CH3)2S]2- Re(CO)4 / The Behaviour of Mono and Diorganylphosphane Sulphides towards Metal Carbonyl Systems, XXI [1] Preparation and Properties of Di[μ-{(dicarbonyl- h5-cyelopentadienylmanganese)- climethylphosphine}thio]-bis(tetracarbonylrhenium), (OC)4Re[h5-C5H5Mn(CO)2P(CH3)2S]2Re(CO)4
Authors: Lindner Ekkehard , Hoehne Sigurd , Rodatz Kurt - Wolfram
Published: February 2015

(OC)4Re[h5-C5H5Mn(CO)2P(CH3)2S]2Re(CO)4 (1) containing a four-membered heterocycle with rhenium sulphur bonds is obtained from Na[h5-C5H5Mn(CO)2P(CH3)2S] and ClRe(CO)5 in THF at 60 °C. The 1H, 31p NMR and IR spectra are discussed. On the basis of x-ray pre­cession photographs both h5-C5H5Mn(CO)2P(CH3)2 groups in 1 are in an anti position.
Darstellung und Kristallstruktur von Silber-Barium-Thiogermanat(IV). Ag2BaGeS4 / Preparation and Crystal Structure of Silver-Barium-Thiogermanate(IV). Ag2BaGeS4
Authors: Teske Chr. L.
Published: February 2015

Ag2BaGeS4 was prepared for the first time and the crystal structure determined using X-ray methods, a - b = 682,g; c = 801,7 pm, Space group I4̅2 m (No. 121) tetragonal. The atomic parameters and interatomic distances are reported and the structure is discussed.
Darstellung und Charakterisierung von chiralen und achiralen exocyclischen π-enyl-Komplexen der Zusammensetzung (C8H13PdCl)2 / Synthesis and Characterization of Exocyclic π-Enyl Complexes of the Composition (C8H13PdCl)2
Authors: Ratka Richard , Ziegler Manfred L. , Schilling Gerhard
Published: February 2015

The mechanism of formation of the exocyclic dimeric π-enyl complex (C8H13PdCl)2 by reaction of 1,3-dimethylenecyclohexane, C8H12 with trans-PdCl2(C6H5CN)2 is discussed. Through UV, 1H NMR (90 MHz, 360 MHz) and 13C spectroscopic studies it was possible to show that the dimer is formed by the disproportionate of C8H12 to C8H14 and m-xylene, and further that it consists of diastereomeric products. The reaction of (-) R-3-methyl-1-methylencyclohexane, C8H14, with the Pd-salt confirms that during the reaction between C8H12 and trans-PdCl2(C6H5CN)2 no free C8H14 is formed in solution.

Studies on cleavage reactions of the dimer are also described in this paper.
Ramanspektroskopische Untersuchungen an festen und in Wasser gelösten Polyboraten / Investigations of Solid Polyborates and their Aqueous Solutions by Raman Spectroscopy
Authors: Janda Ralf , Heller Gert
Published: February 2015

Raman spectra of solid H3BO3, Na2[B4O5(OH)4] · 8 H2O, K[B5O6(OH)4] · 2H2O and Na[B(OH)4] were recorded between 300 and 1500 cm-1 as well as of borax in aqueous solutions as a function of concentration and pH. Because of better solubility in water, the Raman spectrum of ammonium tetraborate in aqueous solution was also recorded as a function of pH. For comparisons the Raman spectra of solid (NH4)2[B4O5(OH)4] · 2 H2O, β-NH4[B5O6(OH)4] · 2 H2O, NH4[B5O6(OH)4] · 0,67 H2O and NH4[B5O6(OH)4] were considered. In solution, all lines in the Raman spectra could be assigned and the degree of depolarization measured. The assigned Raman frequencies can be used for the identification of unknown B-O-lines and therefore of unknown borate or polyborate structures.
Phosphoroxidhalogenid-Komplexe der Uran(IV)-halogenide, UX4 · 2 POX3 (X = Cl, Br), und ein Dichlorophosphat des Uran(VI) / Phosphorylhalide Complexes of the Uranium(IV) Halides, UX4 · 2 POX3 (X = Cl, Br) and a Dichlorophosphate of Uranium(VI)
Authors: Dyck Werner M. , Dehnicke Kurt
Published: February 2015

The complexes UX4 · 2 POX3 (X = Cl, Br) are prepared by the reaction of excess POX3 with the corresponding uranium pentahalides. The dichlorophosphate, CLUO2(O2PCl2) · POCl3, is prepared by treating UCl2 · 2 POCl3 with dichloromonoxide. According to the IR spectra the POX3 solvate molecules are cis coordinated via oxygen. An improved method to prepare uranium pentaehloride is described in detail.
Darstellung und Charakterisierung von cis-und trans-Dihalogeno-bis-acetylacetonato-osmaten(IV) / Preparation and Characterization of cis-and trans-Dihalogeno-bis-acetylacetonato-osmates(IV)
Authors: Preetz W. , Petersen H.
Published: February 2015

Cis-and trans-[OsX2(acac)2], X = Cl, Br, I, are prepared by heating of K2[OsX6] in a 1:1 mixture of acetylacetone: water. The pure stereoisomeres are separated by chromato-graphy on silica gel. The new complexes are characterized by UV-Vis, IR and Raman spectra.
Übergangsmetall-subsituierte Phosphine, Arsine und Stibine, 19 [1]Synthese und einige Eigenschaften übergangsmetall-substituierter Arsinsulfide / Transition Metal Substituted Pliosphines, Arsines and Stibines, 19 [1]Synthesis and Some Properties of Transition Metal Substituted Arsine Sulfides
Authors: Malisch Wolfgang , Janta Reinhard , Künzel Günter
Published: February 2015

The transition metal arsines C5H5(CO)2LM-As(CH3)2 (M = Mo, W; L = CO, P(CH3)3) react with elementary sulfur (selenium) in CS2 to give the transition metal substituted arsine chalcogenides C5H5(CO)2LM-As(CH3)2S(Se). Due to the pronounced basicity of the chalcogen centre they are easily converted into cationic mononuclear complexes [trans-C5H5(CO)2P(CH3)3Mo-As(CH3)2SR]⊕X⊖ by alkylhalides, and into bridged dinuclear complexes tans-C5H5(CO)2P(CH3)3Mo-As(CH3)2S-MLn on treatment with THF · Cr(CO)5 or AgI. The structures of the new compounds are established by spectroscopic investigations.
Studies on Thiocarbonyl Olefination Reactions with Phosphonium Ylides
Authors: Tewari R. S. , Suri S. K. , Gupta K . C.
Published: February 2015

Reactions of several semi-stabilized phosphonium ylides with 2,7-dibromofluorenethione and thiobenzophenone, have been reported to give substituted 9-benzylidene-2,7-dibromo-fluorenes and 1-(substituted phenyl)-2,2-diphenyl ethylenes respectively in fair to good yields. The structural identities were based on spectral data.
Calculation of Acidity Constants of Protonated Weak Organic Bases by a New Method, III* Ethers
Authors: Levitt L. S. , Levitt B. W.
Published: February 2015

It is shown in this paper that a consistent set of values of pKBH⁺ for 24 ethers, in good agreement with the few which have been obtained by other methods, can be calculated from a correlation of the HCl solubility in the ethers with ∑σI of the R groups, and also with the gas phase I.P.'s of the ethers. We find that in solution the order of basicity is ROH>R2O>H2O whereas in the gas phase it is R2O>ROH>H2O. Evidence for complete H+ transfer to R2O is deduced for most cases, but a H-bonding "basicity" occurs for the less basic ethers. A brief review of previously obtained pKBH⁺'s for some ethers, MeOH, and H2O is also presented.
Studies on Spiro Azetidinones and Spiro Thiazolidinones, III Synthesis of Some New Spiro Azetidinones, Spiro Thiazolidinones, Bis-azetidinones and Bis-thiazolidinones
Authors: Hassan Kh. M. , Khalil Z. H.
Published: February 2015

Cyclocondensation reaction of 3-isatylideneoxime (1a), -hydrazone (1b), -phenyl-hydrazone (1c), semicarbazone (1d) and -thiosemicarbazone (1e) with chloroacetyl chloride (and thioglycolic acid) gave the corresponding spiro azetidinones (2) and spiro thiazolidinones (3). 3-Isatylidenehydrazone (1b) was condensed easily with aromatic aldehydes afforded a new 3-isatylidene azomethines (4) which submitted for cyclocondensation reaction with chloroacetyl chloride (and thioglycolic acid) giving bis-azetidinones (5) and bis-thiazolidinones (6), respectively.
Darstellung von Cs3[V(NO)(H2NO)(CN)4] · 2H2O - einem neuen Nitrosyl-oxamido (O,N) Komplex des Vanadins / Preparation of Cs3[V(NO)(H2NO)(CN)4] · 2H2O - a New Nitrosyl-oxamido (O,N) Complex of Vanadium
Authors: Quilitzsch U. , Wieghardt K.
Published: February 2015

The preparation and characterization of Cs3[V(NO)(H2NO)(CN)4] · 2 H20 a nitrosyl-oxamido(O,N) complex of vanadium is reported.
Dimeres Aquo(malonenamidoximato)-(2-ketomalonenamidoximato)-nickel(II) / Dimeric Aquo(malonenamide-oximato)- (2-ketomalonenamide-oximato)-nickel(II)
Authors: Endres Helmut , Nuber Bernhard
Published: February 2015

NiC6H14N8O6 is obtained in a dimeric form, bridged by oxime O atoms, as a by-product during the preparation of bis(malonenamide-oximato)nickel(II). It crystallizes in the mono-clinic space group P21/c with a = 10.053(3), b = 9.338(3), c = 13.392(3) Å, β = 92.09°. The structure was solved by direct and Fourier methods and refined by least squares to R = 0.071 for 2462 intensities.
Ternäre Carbide von Cr, Mo und W mit Platinmetallen / Ternary Carbides of Cr, Mo and W with Platinum Metals
Authors: Holleck Helmut
Published: February 2015

Ternary high temperature carbides were found in the system Cr-Ru-C, Cr-Rh-C, Cr-Ir-C, Cr-Pt-C, Mo-Ru-C, Mo-Rh-C, Mo-Os-C, Mo-Ir-C, Mo-Pt-C, W-Ru-C, W-Rh-C, W-Os-S and W-Pt-C. The com-pounds crystallize in the face centered cubic structure. The carbon content changes systematically with the content and the valence electron concentration of the respective platinum metal.
Studies of the Reaction of Various 1,2-Disubstituted Benzenes with Crotonic Acid in Polyphosphoric Acid
Authors: Grant Hamish G.
Published: February 2015

The reaction of several 1,2-disubstituted benzenes with crotonic acid in polyphosphoric acid has provided a number of previously undescribed 5,6-disubstituted indan-1-ones. Guaiacol, o-cresol, 1,3-benzodioxole, 1,4-benzodioxan and dihydrobenzofuran yielded indanones (4-8) in which acylation of the benzene ring occurred exclusively para to the free hydroxyl groups of the first two substrates and para to the ether oxygen in the last. Catechol, salicylaldehyde, o-hydroxy acetophenone and o-chloro phenol yielded no indanones and formed crotonate esters. A further four indanones (9-12) were derived from demethylation and acetylation procedures. Annelation of the methyl cyclopentanone ring occurred acrose the furan ring in benzofuran to provide the new heterocycle 1-methyl benzofurocyclopentan-3-one in moderate yield. The assigned carbon-13 NMR spectral shifts for all indanones are set out in Table II.
Notizen: Metallorganische Verbindungen der Lanthaniden, VII [1]. Tris(di -t-butylphosphin) derivate von Yttrium, Holmium, Erbium, Thulium, Ytterbium und Lutetium / Organometallic Compounds of the Lanthanides, VII [1].Tris(di-t-butylphosphine)Derivatives of Yttrium, Holmium, Erbium, Thulium, Ytterbium, and Lutetium
Authors: Schumann Herbert , Frisch Georg-Michael
Published: February 2015

Lithium (di-t-butyl)phosphide reacts with the trichlorides of yttrium, holmium, erbium, thulium, ytterbium and lutetium under elimination of lithium chloride and formation of the corresponding tris(di-t-butylphosphine) derivatives.
Notizen: Zur Strukturchemie der Phase Al2O3 · 2 P2O5 · 9 H2O / On the Structural Chemistry of the Phase Al2O3 · 2 P2O5 · 9 H2O
Authors: Kniep Rüdiger , Wilms Axel
Published: February 2015

The crystal structure of the phase Al2O3 · 2 P2O5 · 9 H2O contains two different structural units: isolated PO4 tetrahedra and larger aggregates consisting of two AlO6 octahedra connected with three PO4 tetrahedra by common vertices. Location of hydrogen positions failed. Interpretation of bond distances and molecular symmetry leads to a structural formula

[Al2(H1+xPO4)3(H2O)6](H3-3xPO4);

0 ≦ x ≦ 1

indicating proton disorder. Proton conductivity seems to be possible.
Notizen: Photoaktivierung und Photosensibilisierung des homogenen Hydrierungs -Katalysators IrCl(CO)[P(i-C3H7)3]2 / Photoactivation and Photosensitization of the Homogeneous Hydrogenation Catalyst IrCl(CO)[P(i-C3H7)3]2
Authors: Strohmeier Walter , Stasch Johannes-Peter
Published: February 2015

Under irradiation with monochromatic light of λ ≤ 407 nm homogeneous hydrogenation of acrylic ethylester with the catalyst IrCl(CO)[P(i-C3H7)3]2 is much faster than in the dark reaction. Not the catalyst but the hydridocomplex is photochemically activated. With the sensitizer pentacene, photoactivation occurrs with visible light of λ ≤ 578 nm already.
Komplexchemie polyfunktioneller Liganden, 52 [1]. Hydrido- und Deuterido-mangan(I)-carbonyl-Komplexe des 1.1.1- Tris (diphenylphosphinomeihy 1) ethans / Complex Chemistry of Polyfiinctional Ligands, 52 [1]. Hydrido- and Deuterido-manganese(I)-carbonyl Complexes of 1,1,1 -Tris(diphenylphosphinomethyl)ethane
Authors: Eilermann Jochen , Lindner Helmut A.
Published: February 2015

[Mn(CO)3(R2PCH2)3CCH3]ClO4 (1a) (R = C6H5) reacts with NaBH4 on UV irradiation to yield HMn(CO)2(R2PCH2)3CCH3 (2a). [Mn(CO)3(R2PCH2)3CCH3]BR4 (1b) gives only decomposition products. Boiling of 1a or b and NaOH in acetone/water does nots give 2a but the new hydride HMn(CO)3(R2PCH2)2C(CH3)CH2PR2 (3a). This compound cannot be prepared on ultraviolet irradiation of a solution of 1a or b and NaBH4 in methyl alcohol or acetone. The analogous deutendes DMn(CO)2(R2)PCH2)3CCH3 (2b) and DMn(CO)3(R2PCH2)2C(CH3)CH2PR2 (3b) were also prepared. The new compounds were characterized by their IR, Raman, 1H NMR and 31P NMR spectra.