bluuebunny/crossref_metadata_2025 huggingface dataset:
The Reactions of Alkyl Phosphoramides with Benzene in the Presence of Aluminium Chloride
Authors: Sosnovsky G. , Zaret E. H. , Böhnel B.
Published: March 2015

The reactions of dialkyl N-alkyl phosphoramidates (1) with benzene in the presence of aluminium chloride give aralkyls arising from cleavages of the P-O-C and N-C bonds. Analogous reactions of diphenyl N-alkyl phosphoramidates (2) and triamides (4), (RNH)3P(X), (X = O, S; R = alkyl) also give aralkyls; however, in these cases only N-C bond cleavage occurs. The reaction is not general, i. e., it is limited to phosphoramides derived from primary amines, and no reaction occurs with almost all phosphoramides derived from secondary amines. In addition not all phosphoramides which undergo N-C cleavage yield alkylation products
Notizen: Derivate von 2.6.9-Trioxa-4.8-diaza-1.5-diborabicyclo [3.3.1] nonadien. / Derivatives of 2,6,9-Trioxa-4,8-diaza-1,5-diborabicyclo[3,3,1]nonadiene
Authors: Maringgele Walter , Meller Anton
Published: March 2015

The title compounds, bicyclic B-O-B bridged dimeric amidoboranes, obtained together with substituted halogenoimines by reaction of N-substituted trifluoroacetamides with BCl3 or BBr3, are characterised by 11B and 19FNMR, IR and mass spectra. Possible alternative and/or mesomeric structures are discussed
1: 13- und 1: 14-Heteropolyvanadate des Phosphors(V) / 1:13- and 1:14- Heteropolyvanadates of Phosphorus(V)
Authors: Preuss Fritz , Schug Heinrich
Published: March 2015

Deep red heteropolyvanadates of phosphorus(V) n M2O:P2O5: 13 V2O5 · aq (n = 3, 5, 6; M = Na, K, Rb, Cs, NH4) and n M2O: P2O5: 14 V2O5 · aq (n = 4, 7; M = K, Rb, Cs, NH4, (n-C4H9)4N) were prepared. Recrystallization of 1: 13- and 1: 14-heteropolyvanadates and determination of molecular weight by ultracentrifuge technique in solutions from V2O5 and NaH2PO4 indicate 1: 14-heteropolyvanadate ions to be stable species over a wide range of pH, while 1: 13-heteropolyvanadate ions are only stabilized in higher acidified solutions containing H2PO4
- or as slightly soluble salts. Wide line 1H NMR spectra are interpreted in terms of OH groups and H2O of cristallization, the isolated heteropolyvanadates of both series consisting of protonated anions; the basicity of heteropolyvanadic acids of phosphorus(V) is unknown.
Zum Mechanismus der Substituentenwechselwirkung bei der elektronenstoßinduzierten Äther-Spaltung in para-substituierten Methoxymethylaromaten / On the Mechanism of Substituent Interaction During the Electron Impact Induced Ether Cleavage from para-Substituted Methoxymethyl Benzenes
Authors: Herrmann Rupert , Schwarz Helmut
Published: March 2015

The unusual methyl elimination from para-substituted methoxy-methyl benzenes has been elucidated. It can be shown that two entirely different mechanisms contribute to the reaction: i) intramolecular hydrogen transfer onto the benzene ring (π-complex formation) and ii) substituent migration via ring expansion. Alternative mechanisms as for instance transanular protonation of the ester function or substituent migration via valence bond isomers are not involved in the formation of the [M-methyl]+-ions.
Angular Heterocycles. Synthesis of Some Substituted 6-Chloro-10-trifluoromethylbenzo [a] phenothiazines
Authors: Saxena S. K. , Shukla A. P. , Sadhnani M. D. , Mital R. L.
Published: March 2015

2,3-Dichloro 1,4-naphthoquinone reacts with zinc mercaptide to give 6-chloro-l0-trifluoromethyl-5H-benzo[a]phenothiazin-5-one (1). Synthesis of various O, N acylated and alkylated derivatives (2 to 7) and their sulfoxides (8 to 12) have been described.
Synthesis of Pyridone Derivatives MICHAEL Condensation with Ethyl Cyanoacetate, Cyanoacetamide and Acetoacetamide
Authors: Zoorob H. H. , Ismail E. S.
Published: March 2015

MICHAEL condensation of 2-cinnamoylbenzimidazoles (1 a-h) with ethyl cyanoacetate, cyanoacetamide and acetoacetamide led to the formation of 2(1 H)pyridone derivatives (2 a-c), (3 a-c), 4a-c), and (5 a-c). Compounds (2 a-c) added GRIGNARD reagents at the nitrile group to give 5a-c. CLAISEN condensation of 5 a-c with ethyl acetate gave the corresponding diketo derivatives (6a-c), respectively. Cyclization of 6 b with ethanolic hydrogen chloride gave the 8-azachromone (7). Both 6 and 7 gave the same pyrazole derivative (8) upon the reaction with phenylhydrazine.
Spektroskopische Untersuchungen in der Festkörperchemie, XI 127I-NQR-Untersuchungen an Perjodaten / Spectroscopic Investigations in the Solid State Chemistry, XI 127I NQR Investigations on Periodates
Authors: Burkert Paul K. , Hutter Frank M.
Published: March 2015

A number of periodates show 127I NQR transitions. The correlation of the NQR coupling constants with the length of the unit cell was compared with the results of NQR measurements on perrhenates.
Crystal and Molecular Structure of N-(Trifluorosilyl)trimethylphosphinimine Dimer
Authors: Sheldrick W. S. , Wolfsberger W.
Published: March 2015

N-(Trifluorosilyl)trimethylphosphinimine dimer crystallises in the monoclinic space group P21/n, Z = 2, with a= 6.314(2), b = 12.057(5), c = 10.936(4) Å, β = 95.45(2)°. The structure was solved by direct methods and refined to R 0.078 for 1117 independent reflections. The molecule is dimeric and centrosymmetric with an planar four-membered [SiN]2 ring containing trigonal-bipyramidal pentacoordinate silicon and trigonal nitrogen. Significant differences are observed in the bond lengths from silicon to its equatorial and axial ligands: Si-Neq 1.736(4), Si-Nax 1.857(4), Si-Feq1.606(4) and 1.607(3), Si-Fax 1.668(3) Å. The Si-Neq bond length is similar to that in tetracoordinate derivatives for which a (p →d) π bonding component has been postulated, while the Si-Nax distance is very much shorter than that observed in other pentacoordinate derivatives.
Photochemische 2+2-Cycloadditionen von Äthylen und Acetylen an 1.3-Cyclohexadien unter erhöhtem Druck / Photochemical 2+2-Cycloadditions of Ethylene and Acetylene to 1,3-Cyclohexadiene under High Pressure
Authors: Mirbach Marlis F. , Mirbach Manfred J. , Saus Alfons
Published: March 2015

The photochemical cycloaddition of 1,3-cyclohexadiene (CHD) to ethylene and acetylene at pressures above 10 bar is described. Upon sensitized irradiation (2-acetylnaphthaline) CHD adds to ethylene at room temperature in dichloromethane to give cis-bicyclo[4,2,0]-oct-2-ene (1) along with dimers of cyclohexadiene. The yield of cross adduct increases with ethylene pressure (10-50 bar) whereas dimerisation decreases. Quantum yields of cross addition and dimerisation at 12 M ethylene were determined to be 0.31 and 0.35 respectively. At a pressure of 15 bar acetylene CHD reacts with acetylene to give bicyclo-[4,2,0]octa-2,7-diene (2) and bicyclo[2,2,2]octa-2,5-diene (3) as the major and minor products respectively. In a solvent mixture containing 60 vol-% CH2Cl2 and 40 vol-% acetone (2) is formed with a quantum yield of φ = 0.2. The experimental results are explained by a formal kinetic scheme.
Notizen: Die Kristallstruktur des LiBeAs / The Crystal Structure of LiBeAs
Authors: Tiburtius Christoph , Schuster Hans-Uwe
Published: March 2015

X-ray investigations showed that LiBeAs crystallizes in a modified Fe2As-type-lattice, the cell parameters for the tetragonal phase are a = 3.749 Å, c = 6.219 Å, space group P4/nmm, Z = 2.
Notizen: Addition von Fluorwasserstoff an ein sechsgliedriges C,N,P-Ringsystem / Addition of Hydrogenfluoride to a Sixmembered C, N, P-Ringsystem
Authors: Schöning Georg , Glemser Oskar
Published: March 2015

2,2-Difluoro-4,6-bis(trifluoromethyl)-1,3,5,2λ5-triazaphosphorine adds two moles HF to give a zwitterionic compound involving a hexa-co-ordinated phosphorus atom.
Crystal Structure of Cs2 [Pt(CN)4] · H2O
Authors: Otto H. H. , Schulz Heinz , Thiemann K. H. , Yersin H. , Gliemann G.
Published: March 2015

The crystal structure of Cs2[Pt(CN)4] · H2O has been determined from X-ray diffraction data and refined to a conventional R value of 0.068 from 2210 reflections. The compound is hexagonal, α = 9.687(2) and c = 19.336(6) A, space group C6
2-P 61, Z = 6. The given atomic coordinates represent the absolute configuration. The nearly square planar Pt(CN)42- groups form a helix with respect to the c axis. The distance between neighbouring Pt atoms in the helix is 3.543(1) A. The normal of the Pt(CN)42- group is tilted about 15 deg to the c axis leading to a considerable overlap of metal orbitals which is suggested from optical emission studies. The protons of the water molecules form hydrogen bonds to nitrogen atoms of different helices. Both Cs atoms have similar sevenfold coordination.
Zum Mechanismus der photochemischen Dehydrocyclisierung von Diphenyläther / On the Mechanism of the Photochemical Dehydrocyclisation of Diphenylether
Authors: Zeller Klaus-Peter , Gauglitz Günther
Published: March 2015

The photochemical cyclisation of diphenylether to dibenzofuran is scavenged by trans-1,3-pentadiene indicating that the triplet state of the ether is the reactive species. The intramolecular, kinetic isotope effects kʜ/kᴅ for the cyclisation of 2-deuteriodiphenyl ether and 1-phenoxy-4-pentadeuteriophenoxy-benzene are 1.12 ± 0.05 and 1.19 ± 0.05, respectively. A reaction scheme consisting of a photochemical cyclisation to 1 a, 9 a-dihydrodi-benzofuran followed by dehydrogenation to dibenzofuran is suggested.
Pyrimidine Derivatives and Related Compounds, V Synthesis of Some Isoxazolo [2,3-a] pyrimidines. A New Ring System
Authors: Elnagdi Mohamed Hilmy , Kandeel Ezzat Mohamed , Sadek Kamal Usef
Published: March 2015

3-Amino-5-phenyl-4-phenylazoisoxazole (1) reacts with ethyl acetoacetate to yield the corresponding ethyl isoxazolylaminocrotonate derivative (2) which could be thermally cyclized into the isoxazolopyrimidine derivative (4). On the other hand, condensation of 1 with ethoxymethylenemalononitrile has resulted in the formation of the aminoethylene derivative (5).

Compound 1 reacted with acrylonitrile to yield the isoxazolo[2,3-a]pyrimidine derivative (6). The latter was converted into the corresponding exo derivative (8) by the action of acetic acid-hydrochloric acid mixture.

Compound 1 also reacted with methoxycarbonyl-, ethoxycarbomyl- and benzoyl isothiocyanates to yield the isoxazolylthioureas (10a, b) and (11), respectively. The reaction of 2 with acetic acid-hydrochloric acid and with phenylhydrazine is reported.
Notizen: Beiträge zur Chemie des Phosphors, 7l1 Zur Existenz von Phosphor-selenid-tribromid PSeBr3 / Contributions to the Chemistry of Phosphorus, 711About the Existence of Phosphorus Selenide Tribromide PSeBr3
Authors: Baudler Marianne , Volland Bernd
Published: March 2015

The title compound is formed in low concentration by addition of selenium to PBr3 or by reaction of (CH3Se)PBr2 with bromine.
Notizen: Kristallstruktur eines mesomeren Organozinnradikals1 / Crystal Structure of a Mesomeric Organo Tin Radical
Authors: Uber Wolfgang , Stegmann Hartmut B. , Scheeffleb Klaus , Strähle Joachim
Published: March 2015

o-Aminophenols react with organo tin compounds forming stable mesomeric complexes. The structure of one compound was determined by X-ray crystallography. The tin atom is chelated by two oxygen and one nitrogen atom. The nitrogen atom and the associated C and Sn atoms are in a plane and therefore the ESR tin coupling constant has an additional contribution by a π-σ-interaction through the N—Sn bond.
Beiträge zur Chemie von Molybdän und Wolfram, XIX Zur Lage der Η-Atome in MoO2C2 · H2O / Contributions to the Chemistry of Molybdenum and Tungsten, XIX The Positions of Η-Atoms in MoO2Cl2 · H2O
Authors: Schröder F. A.
Published: March 2015

By calculating MAPLE, it can be discriminated between 2 alternatives of the H positions of an O-Η···Cl bridging system. Application of this result on a polytype crystal of this compound leads to further alternatives which are discussed. The existence of the polytype crystal cannot be explained by the H bridging system but only by the conditions during crystal growth.
Beiträge zur Chemie von Molybdän und Wolfram, XX Verfeinerung der Kristallstruktur der roten Molybdänbronze — K0,33MoO3 / Contribution to the Chemistry of Molybdenum and Tungsten, XX Refinement of the Crystal Structure of the Red Molybdenum Bronce - K0,33MoO3
Authors: Schröder F. A. , Schuckmann W.
Published: March 2015

With new X-ray data from a crystal of stoichiometric K0.33MoO3 the crystal structure of this compound was refined until R(anisotropic) = 0.023. The characteristic distortion of the Mo-O octahedra is discussed.
Mössbauer-spektroskopische Untersuchungen an Na2MnFeF7 / Mössbauer Spectroscopic Investigation of Na2MnFeF7
Authors: Pebler J. , Schmidt K. , Babel D. , Verscharen W.
Published: March 2015

In contrast to the Mössbauer spectrum of the orthorhombic compound Na2NiFeF7 that of the manganous compound Na2MnFeF7 gives evidence of two different iron positions. This rules out Na2MnFeF7 to be isostructural with Na2NiFeF7, which crystallizes like most compounds Na2MIIMIIIF7 in the weberite structure, the MIII ions occupying only one site in space group Imm 2-C2v
20.

The Mössbauer data evaluated for the two iron sites (Fe 1/Fe 2 respectively) in Na2MnFeF7 are: θ = 0/90°, φ = undetermined/70°, η = 0.6 both, Η = 551/541 kOe, Vzz = ± 2.7 · 1018 Vcm-2 both. NaMnFeF7 is antiferromagnetic with a Neél temperature of TN = 94 Κ for both iron positions.
Effect of Temperature on the Electrode Kinetics of Totally Irreversible and Quasi-Reversible Polarographic Reductions
Authors: Sharma Sudhindra Swarup , Jha S. K. , Singh Mukhtar
Published: March 2015

The polarographic behaviour of Ni(II), Co(II), Zn(II) and Mn(II) has been studied in 0.1 M KNO3. The temperature span studied varies from 15 to 55 °C. The reduction of Ni(II) and Co(II) has been found to be totally irreversible and that of Zn(II) and Mn(II) quasi-reversible over the temperature span studied. The kinetic parameters, kf,h
0 and ana for the totally irreversible reductions have been calculated by KOUTECKY’S treatment while for quasi-reversible reduction the kinetic parameters (a and ks,h) have been evaluated by GELLINGS’ method. The activation energy of the totally irreversible reductions has also been determined. The effect of temperature has been discussed in terms of the variations in the values of the kinetic parameters.
Pyrimidine Derivatives and Related Compounds, VII Synthesis of Some New Pyrazolo [1,5-a] -S-triazines, Pyrazolo [3,4-c] -as-triazines, Pyrazolo [1,5-a] pyrimidines and Pyrazolo [3,4-b] pyrones
Authors: Elnagdi Mohamed Hilmy , Zayed Ezzat Mohamed , Kandeel Ezzat Mohamed , Fahmy Sherif Mahmoud
Published: March 2015

3-Amino-4-phenylhydrazono-2-pyrazolin-5-one (1) reacts with isothiocyanate to yield the corresponding pyrazolylthiourea derivatives (2 a-c). Whereas 2 a reacted with hydrazines to yield the pyrazolylamino-1,2,4-triazoles (3 a, b), it cyclised into the pyrazolo-[3,4-e]-as-triazine derivative (4) upon treatment with concentrated sulphuric acid. On the other hand, the pyrazolo[1,5-c]-S-triazine derivative (5) was formed from reaction of 2a with ethanolic sodium ethoxide.

3-Amino-2-pyrazolin-5-one (8) reacted with ethyl acrylate to yield a mixture of the 4-dialkylated derivative (9) and the pyrazolo[3,4-b]pyrone (11). Compound 11 could be converted into the corresponding pyrazolo[3,4-b]pyrones (12) and (13) by the action of acetic acid hydrochloric acid mixture and of concentrated sulphuric acid, respectively.
Darstellung, Schwingungsspektren und Röntgenstrukturanalyse von Trifluor- und Trichloracetyltrischwefeltrinitrid, CX3CO-NS3N2
1 / Synthesis, Vibrational Spectra, and X-ray Structure Analysis of Trifluoro and Trichloroacetyl Trisulfurtrinitride, CX3CO—NS3N2
1
Authors: Steudel Ralf , Rose Fritz , Reinhardt Richard , Bradaczek Hans
Published: March 2015

S4N4 reacts at 25 °C with trifluoro and trichloro acetic acid anhydride, respectively, to yield yellow crystalline CX3–CO–NS3N2 (X = F, Cl), the mass, infrared, and Raman spectra of which are reported. An X-ray structure analysis of monoclinic CF3CONS3N2 revealed a non-planar five-membered S3N2 ring containing an unusually long (2.206 A) sulfur-sulfur bond with one sulfur atom additionally connected to an exocyclic nitrogen atom by a multiple bond. Comparisons with the infrared spectra of S3N2O and ten compounds of type RNS3N2 allowed to identify four wavenumbers characteristic for the S3N2 ring. The relationship μ = 23.09d-27.27 has been derived for stretching vibrational wavelengths, μ (in μm), and bond distances, d (in Å), of sulfur-nitrogen bonds.
Untersuchung der M1-Phase des V1-xFex02-Systems / Investigation of the M1-Phase in the System V1-xFexO2
Authors: Pebler J. , Schmidt K. , Wasinski H.
Published: March 2015

The Mössbauer effect of 57Fe has been studied in the series of compounds Vi1-xFexO2 for very low Fe concentrations between 4.2 and 500 K. Three insulating phases are clearly distinguished. In the low temperature M1-phase only one Fe-site is seen for x ≦ 0.0026 in accordance with the insulating phase of VO2. But for higher Fe concentrations, x ≧ 0.006, two iron sites can be resolved by their electric field gradients in the M1-phase. The Debye-Waller factor shows an anomalous behaviour for both iron concentrations in the M1-phase.
NMR-Untersuchungen an Organoelement(IVb)-phosphinen, II1 Substituenteneinflüsse auf die 31P-chemischen Verschiebungen von Trimethylelement(IV b) -phosphinen / NMR-Studies on Organoelement(IVb)-phosphines, II1 Influence of Ligands on the 31P-Chemical Shift of Trimethylelement(IVb)-phosphines
Authors: Schumann Herbert , Kroth Heinz-Jürgen
Published: March 2015

The 31P-chemical shifts of trimethylsilicon-, -germanium-, and -tinphosphines of the type [(CH3)3E]nPR3-n (E = Si, Ge, Sn; R = H, tC4Η9, C6H5; n = 0, 1, 2, 3) are reported and discussed.
Linear Chain Bis(α,β-dionedioximato)metal Compounds of the Nickel Triad: Solid State Design by Molecular Engineering
Authors: Endres H. , Keller H. J. , Lehmann R. , Poveda A. , Rupp H. H. , Sand H. Van De
Published: March 2015

Chemical and structural data of numerous bis(α,β-dionedioximato)metal(II) compounds are summarized. All of them crystallize in columns but principally two different kinds of molecular arrangements occur in the solids. In one phase the molecular planes are inclined to the direction of the linear metal chains with an angle different from 90°. This allows only indirect interactions between the metal ions via the ligand. (“M—L—M” stacking.) The other modification consists of molecules with their planes perpendicular to the M—M-chains. This form allows direct metal-metal contacts (“M—M” modification). Depending on a few molecular parameters a “M—L—M” or a “M—M” stacking is obtained upon crystallization. Since for those compounds which could be isolated in both modifications the M—L—M form has the higher density it is concluded that only stronger M—M interactions stabilize the less dense M—M forms.

A wide range of metal-metal separations with a lower limit of 3.15 Å in mixed valence systems are found in different “M—M” compounds. In any case the intrachain metal-metal distances are reduced considerably upon oxidation of the bivalent complex molecules. The influence of “electronic” and “sterical” parameters of the complex molecules on the intermolecular metal interactions and on the type of columns in the solid state is discussed.
Reactions of Dichloroxozirconium(IV) Octahydrate with Monocarboxylic Acid Chlorides
Authors: Chand Paul Ram , Gupta Surinder Kumar , Dev Sharma Rajendra , Vasisht Sham Kumar
Published: March 2015

Dichloroxozirconium(IV) octahydrate reacts with acetyl, propionyl, butyryl and chloracetyl chlorides at low temperatures to form addition compounds of the parent carboxylic acid, ZrOCl2 · 2 RCO2H, but at higher temperatures the corresponding carboxylates of the type ZrO(RCO2)2 · RCO2H are obtained. Benzoyl chloride does not react at low temperatures, but at 60 °C gives an addition product ZrOCl2 · 2 C6H5CO2H, and at higher temperatures a substitution product ZrO(C6H5CO2)2 · 2 C6H5CO2H is obtained. Elemental analyses, molar conductance measurements, infrared spectral studies and thermal decompositions have been carried out to understand the nature of these compounds.
Chemical Ionization Mass Spectrometry: A Useful Stereochemistry Probe
Authors: Van de Sande C. C. , Van Gaever F. , Sandra P. , Monstrey J.
Published: March 2015

The helium charge exchange and the isobutane chemical ionization spectra of 4-methoxy cyclohexanecarboxylic acid ethyl esters (1c and 1t), 2,6-dimethyl-4-hydroxytetrahydropyranes (2c and 2t), 2,4,6-trimethyl-4-hydroxytetrahydropyranes (8c and 3t), and 2,7-dimethoxy-cis-decalins (4c and 4t) have been screened for correlations with the stereochemistry of these molecules. From these data it appears that chemical ionization is especially suited for configurational assignments in epimeric molecules.
Notizen: Reaktionen des Tris(trimethylsilyl)hydroxylamins mit Schwefel- und Phosphoroxidfluoriden / Reactions of Tris-trimethylsilyl Hydroxylamine with Oxifluorides of Sulfur and Phosphorus
Authors: Lidy Werner , Jäckh Christof , Sundermeyer Wolfgang
Published: March 2015

The new compounds R3Si-O-NSOF2 and R3Si-O-N(SiR3)POF2 [R = CH3] are obtained by cleavage reaction of Si-N-bonds in tris(trimethylsilyl)hydroxylamine by OSF4 and OPF3, respectively.
Resonanz-Raman-Spektren von trans-Tetrahalogenodicarbonylosmaten(III) / Resonance Raman Spectra of trans-Tetrahalogenodicarbonylosmates(III)
Authors: Johannsen F. H. , Preetz W.
Published: March 2015

The Raman spectra of (TBA)-trans[OsX4(CO)2] salts (X = Br, I; TBA+ = Tetrabutylammonium) show up to nine overtones and many combination tones of the totally symmetric stretching modes ν(OsX), ν(OsC) and ν(CO). The intensities of the overtones depend on the electronic spectra. The anharmonicity of the vibrations is small. All fundamentals are assigned by IR and Raman data.
Die Kristallstruktur von Li2 Ga und Li3Ga2 / The Crystal Structure of Li2Ga and Li3Ga2
Authors: Müller Wiking , Stöhr Joachim
Published: March 2015

Li2Ga crystallizes orthorhombic, space group Cmcm—D17
2h, a = 456.2(2), b = 954.2(5) and c = 436.4(2) (pm). The Ga substructure consists of zig-zag-chains. Li3Ga2 is isotypic with Li3Al2: trigonal-rhomboedric, space group R3̅m—D3
5d, α = 436.7(1), c = 1389.6(5), the Ga atoms forming layers of puckered six-membered rings. Both phases crystallize in an ordered variant of the bcc packing. Relations to the phases with the same packing in the systems Li-Αl and Li—Sn are discussed.
Notizen: Darstellung von Tetramanganhexadekacarbonyl / Preparation of Tetramanganesehexadecacarbonyl
Authors: Jaitner Peter E. , Schwarzhans Karl E.
Published: March 2015

Tetramanganesedecahexacarbonyl has been prepared. The configuration of this polynuclear carbonyl has been derived by IR-and mass-spectrometric measurements.
Notizen: γ-Radiolysis of N-Acetyl-D-glucosamine in the Solid State
Authors: Bradbury Allan G. W. , Sonntag Clemens Von
Published: March 2015

In the γ-radiolysis of polycrystalline N-acetyl-D-glucosamine 19 products have been identified and their G-values determined. Major products are 2-acetamido-2-deoxyhexodialdose (G = 1.2) and 2-acetamido-2,5-dideoxyhexodialdose (G = 1.1). It is suggested that the high radiation sensitivity of mucopolysaccharides with respect to biological effects is probably not due to extraordinary high G-values.
Heterocyclic Compounds Synthesis of 7,14-Diacetyl-3,10-diethoxy-6,13-dihalo-triphenodithiazine and Derivatives
Authors: Jain Surendra Kumar , Mital R. L.
Published: March 2015

7,14-Diacetyl-6,13-dihalo-3,10-diethoxytriphenodithiazines have been synthesised by reductive acetylation of 6,13-dihalo-3,10-diethoxytriphenodithiazine with Zn dust (Ac2O) pyridine. Attempts to synthesis 7,14-dihydro-6,13-dihalo-3,10-diethoxytriphenodithiazine is failed. Oxidation with 30% H2O2 in AcOH of 7,14-diacetyl-6,13-dihalo-3,10-diethoxytriphenodithiazine did not produce its S,S-dioxide. 3-Acetoxy-7-ethoxy-1,2,4-trihalophenothiazine on treatment with 30% H2O2 in AcOH regenerated 7-ethoxy-1,2,4-trihalo-3H-phenothiazine-3-one by oxidative deacetylation. Their Ri values and IR spectral data have been recorded.
Notizen: CaFe6Al6O19 mit Magnetoplumbitstruktur / CaFe6Al6O19 with Magnetoplumbite Structure
Authors: Harder M. , Müller-Buschbaum Hk.
Published: March 2015

Single crystals of the hitherto unknown compound CaFe6Al6O19 were examined by X-ray work. It is isotypic with the magnetoplumbite structure (a = 562.8, c = 2208. 4 pm, space group D6h
4-P63/mmc). A discussion of the statistical distribution of Fe3+ and Al3+ with respect to other compounds of this type is given.
Darstellung und Untersuchung neuer komplexer Jodoverbindungen von Quecksilber / Preparation and Study of New Complex Iodo Acids of Mercury
Authors: Galinos A. G. , Perlepes S. P.
Published: March 2015

The preparation, for the first time, of the complex iodo acids of mercury (II) with ether and pyridine of the formula H[HgI3]2B (where B = ether or pyridine) is described. The chemical and physical properties of these acids and the UV and IR spectra of the pyridine compound are reported and discussed.
Synthesen mit Nitrilen, XLVIII Merocyanine und Oxonole von Phenyl-indanyliden-acetonitrilen / Syntheses with Nitriles, XLVIII Merocyanines and Oxonoles of Phenyl-indanylidene-acetonitriles
Authors: Junek Hans , Fischer-Colbrie Herwig , Hermetter Albin
Published: March 2015

2-Dicyanomethylene-1,3-indandione reacts with 2,6-disubstituted anilines to give aminophenyl-1,3-dioxo-2-indanyl-malononitriles. By heating or by photolysis HCN is eliminated from the adducts and deeply coloured aminophenyl-1,3-dioxo-2-indanylideneacetonitriles are formed. They are classified as merocyanine type polymethines. The irreversible change in colour occurs at temperatures above 70 °C, the adducts are therefore capable of indicating temperatures. Reaction of phenols with 2-dicyanomethylene-1,3-indandione yields hydroxyphenyl-1,3-dioxo-2-indanylideneacetonitriles, oxonole type polymethines with the properties of pH-indicators.
Über die Reaktionen von Na2[M2 (CO)10] (M = Cr, Mo, W) mit GeX4 und SnX4 (X = Cl, Br, I) / On the Reactions of Na2[M2(CO)10] (M = Cr, Mo, W) with GeX4 and SnX4 (X = Cl, Br, I)
Authors: Behrens Helmut , Moll Matthias , Sixtus Eduard
Published: March 2015

(OC)5M-GeX2 · THF and (OC)5M-SnX2 · THF are formed by the reactions of disodium decacarbonyl dimetallates of 6 b metals with the tetrahalides GeX4 and SnX4:

Na2[(OC)5M-I-M-I(CO)5] + EX4[xxx](OC)5M-II-EX2· THF [xxx] Na[M°(CO)5X]

(M = Cr, Mo, W; E = Ge, Sn; X = Cl, Br, I).
Thiokohlensäure-Komplexe von Metallen der VI. Nebengruppe / Thiocarbonic Acid Complexes of Group VI Metals
Authors: Lindner E. , Nagel W.
Published: March 2015

The new complexes (OC)5MSC(X)Y (8-5) are obtained by reaction of (OC)5MTHF (1) [M = Cr (a), Mo (b), W (c)] with different thiocarbonate, thiourea and thiourethane ligands S = C(X)Y (2a-h). Structure and bonding conditions are discussed on the basis of their IR and 13C NMR spectra. From the spectroscopic data the ligands 2a-h can be arranged in a row with increasing π-acceptor properties.
Etherate and Pyridine Compounds of Mixed Complex Halo Acids of Indium(III) with Thiocyanate
Authors: Galinos A. G. , Zafiropoulos Th. F.
Published: March 2015

The preparation, for the first time, of ether and pyridine compounds of mixed complex halo acids of indium(III) with thiocyanate is described.

The study of the chemical and physical properties of these acids and the UV and IR spectra of the pyridine compounds are also reported and discussed.
Notizen: Darstellung von (NSOCl)3 aus Natriumazid und Thionylchlorid / Preparation of (NSOCl)3 from Sodium Azide and Thionyl Chloride
Authors: Klüver H. , Glemser O.
Published: March 2015

The preparation of (NSOCl)3 from sodium azide and thionyl chloride is described.
Heteronukleare Clustersysteme, X (CO)9Co3M(CO)2(η-C5H6) (M = Mo, W) — Synthese, Eigenschaften und Struktur von Molybdän- und Wolfram-haltigen Trikobaltnonacarbonyl-Clustern / Heteronuclear Cluster Systems, X (CO)9Co3M(CO)2(η-C5H5) (M = Mo, W) — Synthesis, Properties and Structure of Molybdenum and Tungsten Containing Tricobaltnonacarbonyl Clusters
Authors: Schmid Günter , Bartl Klaus , Boese Roland
Published: March 2015

The synthesis of (CO)3(η-C5H5)M—Co(CO)4 and the cluster-compounds

(CO)9Co3M(CO)2(η-C5H5) (M = Mo, W)

is described. IR, 1H—NMR and mass spectroscopic data are discussed. The structure of (CO)9Co3Mo(CO)2(η-C5H5) was solved by X-ray analysis.
Über die Wirkung von Ozon auf Maleinsäure, Fumarsäure und deren Oxidationsprodukte in wäßriger Lösung / Reactions of Ozone with Maleic Acid, Fumaric Acid and with their Oxidation Products in Aqueous Solution
Authors: Gilbert Ernst
Published: March 2015

The ozonation of maleic acid in aqueous solution (pH 3) leads to the formation of glyoxylic acid and formic acid which are oxidized to the stable endproducts oxalic acid and CO2 in the further course of the reaction.

With fumaric acid besides the double bond cleavage (75%) an anomalous ozonolysis is observed leading to the formation of the unstable intermediate mesoxalic acid semialdehyde which is oxidized to mesoxalic acid.

In both cases 45% of the organic carbon appear as CO2 after the complete elimination of the initial compounds. The specific ozone consumption in our experiments was 4 mmol O3 per mmol of acid.

On account of the quantitative follow up of the oxidation products the reaction mechanisms are discussed. The oxidation of glyoxylic acid, formic acid, oxalic acid and mesoxalic acid as pure substances by ozone gives qualitatively the same results as in the mixtures.
Amines as Dehalogenating Agents, IIΙ The Fate of Ν,Ν-Dimethylaniline in the Reductive Dehalogenation of 3-Bromocamphor
Authors: Giumanini Angelo G. , Musiani Marco M.
Published: March 2015

A product analysis was made for the reaction between some aromatic amines and 3-bromocamphor (2), which was invariably transformed into camphor (3) and eventually aryliminocamphor. The tertiary N,N-dimethylanilines were oxidized through a complex sequence of couplings and rearrangements to a number of diamines of the diphenylmethane type. Aniline (4) was also successful in the reductive debromination of 2 to 8 and camphor anil (7), but gave only tarry amino compounds. The reaction, carried out at 200 °C, appeared most probably to be triggered by the radicalic dissociation of the C-Br bond. Bromine ended up as bromide ion in a quantitative fashion.
Arylierungsreaktionen mit Aryldiazosulfonen / Arylation Reactions of Aryldiazosulfones
Authors: Kreher Richard , Halpaap Reinhard
Published: March 2015

The reaction of aryldiazo-4-tolylsulfones with benzene under the influence of aluminiumchloride has been investigated. Elimination of p-toluene-sulfinic acid is followed by evolution of nitrogen; substituted biphenyls can be isolated as main products. Aryl- and biphenylyl-4-tolyl-sulfoxides are formed by a consecutive process of the sulfinic acid as minor products. The arylation reaction presumably proceeds via the intermediate formation of aryl-diazonium ions.
Die Molekiilstruktur von 11-Oxo-1.11-diphenyl-dibenzo [b.g] -indeno [2.3-d] -11.15 b-dihydrophosphocin / The Molecular Structure of / 11-Oxo-1,11-diphenyl-dibenzo[b,g]-indeno[2,3-d]-11,15 b-dihydrophosphocin
Authors: Winter Werner
Published: March 2015

The title compound crystallizes in the monoclinic space group P 21/c with four molecules in the unit cell of dimensions a = 8.88(1), b= 20.86(3), c =14.14(2) Å, β= 111.27(5)°.

The structure was determined by direct methods and refined to R = 0.046 (1777 independent reflexions). The eight-membered phosphorus-carbon-heterocycle has a boatconformation and the phenyl-substituent occupies the quasi-axial ring-position.
Notizen: Darstellung von wasserfreiem KBiO3 / Preparation of Anhydrous KBiO3
Authors: Jansen Martin
Published: March 2015

Anhydrous KBiO3 was obtained for the first time; the synthesis was achieved by solid state reaction using high oxygen pressures. KBiO3 is isostructural to KSbO3, a = 10.016(4) A.
Notizen: Zur Darstellung und Struktur von A3Al2Si2 (A=Ca, Sr, Ba) / Preparation and Structure of A3Al2Si2 (A = Ca, Sr, Ba)
Authors: Wideba Axel , Schäfer Herbert
Published: March 2015

The compounds A3Al2Si2 (A = Ca, Sr, Ba) are isotypic to the analogous Ge-compounds and crystallize in an ordered variant of the Ta3B4-structure type.
Notizen: Darstellung und Kristallstruktur von α- und β-Cu3TiO4 / Preparation and Crystal Structure of α- and β-Cu3TiO4
Authors: Range Klaus-Jürgen , Ketterl Fritz
Published: March 2015

A compound Cu3TiO4 was found to exist in the ternary system CuO-Cu2O-TiO2. The crystal structures of two modifications are very similar and contain Cu+ with linear, Cu2+ and Ti4+ with trigonal distorted octahedral coordination.
Die Kristallstruktur des Nitridotetrachloromolybdat(VI), [(C6H5)4As] [MoNCl4], und die Hydrolyse zum isotypen Oxotetrachloromolybdat(V), [(C6H6)4As] [MoOCl4] / The Crystal Structure of the Nitrido Tetrachloro Molybdate(VI), [(C6H5)4As][MoNCl4], and the Hydrolysis to the Isotypic Oxo Tetrachloro Molybdate(V), [(C6H5)4As][MoOCl4]
Authors: Knopp Brigitte , Lörcher Klaus-Peter , Strähle Joachim
Published: March 2015

The partial hydrolysis of AsPh4[MoNCl4] (AsPh4 = [(C6H5)4As]) leads to AsPh4[MoOCl4]. Both salts crystallize isotypic in the tetragonal space group P 4/n with Z = 2. The crystal structures are built up by AsPh4 cations and square pyramidal [MoXCl4] anions with the symmetry C4v. The Mo—N distance of 166 pm and the slightly longer Mo-O distance of 171 pm indicate strong π-bonding.
Borverbindungen, 8. Mitteilung Umlagerung mittlerer O-B-O-Heterocyclen zu ringförmigen Oligomeren / Boron Compounds, Part 8 Rearrangement of Medium Sized O-B-O Heterocycles to Cyclic Oligomers
Authors: Gerwarth Ulrich W.
Published: March 2015

The condensation of phenyldihydroxyborane with pentane-1,5-diols yields no 1,3,2-dioxabora-cyclooctanes but oligomeric boron heterocycles. Their formation can be explained by an exchange of ligands of the boron atom, a process analogous to metathetic ring-opening polymerisation.
Mössbauer-Untersuchungen an Eisencarbonylkomplexen mit Carben-, Alkoxycarbonyl- und Carbamoylliganden / Mössbauer Investigations of Iron Carbonyl Complexes with Carbene, Alkoxycarbonyl and Carbamoyl Ligands
Authors: Pebler Jürgen , Petz Wolfgang
Published: March 2015

The Mössbauer parameters of (CO)4FeL complexes were determined, were L are carbon ligands. The isomer shifts show strong π-interactions, if backbonding from the substituenta of the carbon atom is possible. The quadrupole splitting of [(CO)4FeCONMe2]2Ni indicates a coordination number of six for the iron atoms with iron-nickel interactions.
Cis- und trans-Isomere des 1.5-Dimethyl-3.6-diphenoxy-3.6-dithioxo-1.2.4.5-tetraza-3.6-diphosphacyclohexans (des 1.5-Dimethyl-3.6-diphenoxy-3.6-dithioxocyclodi(phosphadiazans)) / Cis- and trans-Isomers of 1,5-Dimethyl-3,6-diphenoxy-3,6-dithioxo-1,2,4,5-tetraza-3,6-diphosphacyclohexane (of 1,5-Dimethyl-3,6-diphenoxy-3,6-dithioxocyclodi(phosphadiazane))
Authors: Engelhardt Udo , Merrem Hans-Joachim
Published: March 2015

C6H5O-(S)P(N(CH3)-NH2)2 reacts with C6H5O(S)PCl2 to give the title compound. The cis- and trans-isomers of this product have been separated and are characterized by their IR, 1H NMR and 31P NMR spectra.
A Convenient Synthesis of Naphthazarin and Naphthopurpurin
Authors: Lewis John R. , Paul John
Published: March 2015

A high yielding synthesis of naphthazarin or naphthopurpurin can be achieved by SnCl2 reduction of 2,3-dichloronaphthazarin followed by oxidation in the absence or presence of KO2. The spectral properties of these compounds are discussed.
Notizen: Eine nene Synthese für MoNCl3 / A New Synthesis of MoNCl3
Authors: Dehnicke Kurt , Weiher Ulrich , Strähle Joachim
Published: March 2015

MoNCl3 is prepared by the reaction of Mo(CO)6 with NCl3 in CCl4-solution with good yields.
Notizen: Zur Darstellung und Kristallstruktur von Mg5Al2Ses / On the Preparation and Crystal Structure of Mg5Al2Se8
Authors: Dotzel Klaus-Peter , Schäfer Herbert
Published: March 2015

The new ternary selenide Mg5Al2Se8 has been prepared and structurally characterized. It crystallizes orthorhombic with

α = 1330 ± 3 pm, b = 632 ± 2 pm and

c = 772 ± 2 pm,

space group Pna21–C

. The relations to the Mg2SiO4 and Li3PO4 structure are demonstrated.
neuer substituierter ƞ5 -Cyclopentadienyl-ruthenium-carbonyl-Kationen / Syntheses and Spectral Data of New Substituted ƞ5 -Cyclopentadienyl Ruthenium Carbonyl Cations
Authors: Jungbauer Anton , Behrens Helmut
Published: March 2015

The syntheses and the IR and 1H NMR spectra of the new cations [ƞ5-C5H5Ru(CO)2L]+(L=CH3CN, propene, cyclohexene, PPh3, PEt3, NH3,CNCH3) , {[ƞ5-C5H5Ru(CO)2]2PP}2+ and [ƞ5-C5H5Ru(CO)PP]+ (PP=Ph2PCH2CH2PPh2) are described.
Notizen: Convenient Preparation and Vibrational Spectra of Cyclodecasulfur, S10, and of the Adduct S6 · S10 [1]
Authors: Steudel Ralf , Steidel Jürgen , Sandow Torsten , Schuster Fritz
Published: March 2015

Thermal decomposition of S6O2 and S7O, respectively, in CH2Cl2 or CS2 solution at temperatures between 20 and 5 °C yields SO2, polymeric sulfur and S10 which was obtained as pure single crystals in yields of 7-11% with regard to the starting materials S6 and S7, respectively. Infrared and Raman spectra of S10 as well as of the new molecular addition compound S6 · S10 are reported.
Selbststapelnde Systeme, I 4,4′,5,5′-Tetramethoxy-2,2′-dithiobiphenyl-Iod (6/7), eine Verbindung mit Radikalkationen und Polyiodidketten / Selfstacking Systems, I 4,4′5,5′-Tetramethoxy-2,2′-dithiobiphenyl-Iodine (6/7), a Compound with Radical Cations and Polyiodide Chains
Authors: Hinrichs Winfried , Kopf Jürgen , Stender Klaus-Wilhelm , Klar Günter
Published: March 2015

The title compound can be isolated from concentrated solutions of 4,4′,5,5′-tetramethoxy-2,2′- dithiobiphenyl (DTB, 2) and iodine as blue needles with brass-coloured luster. The crystal structure consists of stacks of (partially oxidized) DTB units with alternating orientations and of disordered polyiodide chains in channels between these stacks. The DTB molecule is not planar; the dihedral angle between the two phenyl rings is 25.1°, the dithio bridge is inclined by 41.7° to the longitudinal axis. The bond distances and angles of the disulfide group are in the normal range, the dihedral angles (CArSS′CAr′ = 55.6°, CArCArSS′ = 41.3°) differ from the ideal values of ca. 90° as a consequence of the cyclic structure
Reaktiviät von Metall–Metall-Mehrfachbindungen, II [1] Nukleophile Addition von Methylensulfiden an [CpMo(CO)2]2 unter Bildung von Cp(CO)2Mo(μ-S(CH2)n)Mo(CO)2Cp-Spezies; Röntgenstrukturanalyse von Cp(CO)2Mo(μ-S(CH2)6)Mo(CO)2Cp / Reactivity of Metal-Metal Multiple Bonds, II [1] Nucleophilic Addition of Methylenesulfides to [CpMo(CO)2]2 with Formation of Cp(CO)2Mo(μ-S(CH2)n) Mo(CO)2Cp Spezies; X-Ray Structure Analysis of Cp(CO)2Mo(μ-S(CH2)6)Mo(CO)2Cp
Authors: Blechschmitt Klaus , Guggolz Ernst , Ziegler Manfred L.
Published: March 2015

The triply Mo-Mo bonded molecule [Cp(CO)2Mo]2 was reacted with the cyclic sulfides S(CH2)n (n = 4-6). The species Cp(CO)2Mo(μ-S(CH2)n)Mo(CO)2Cp were isolated and characterized by their analytical and spectroscopic data. X-Ray structure analysis of the compound Cp(CO)2Mo(μ-S(CH2)6)Mo(CO)2Cp proved the cyclic sulfide to act as a bridging ligand
Sonolysis of Carbon Dioxide, Nitrous Oxide and Methane in Aqueous Solution
Authors: Henglein A.
Published: March 2015

Water was irradiated with ultrasonic waves under an argon atmosphere which contained small amounts of carbon dioxide, nitrous oxide or methane. The yield of the products was measured as a function of the composition of the gas atmosphere. Maximum yields were observed at a few per cent of the added polyatomic gas. No chemical effects occurred in the irradiation under an atmosphere of pure CO2 , N2O or CH4. It is concluded that the gas mixture in the tiny gas bubbles, in which the chemical effects are brought about, is not in Henry’s equilibrium with the aqueous gas solution.

The main product of the sonolysis of CO2 is CO, a small amount of formic acid also being formed. The sonolysis is explained by both the attack of H atoms from the sonolysis of water and direct decomposition of CO2 due to the high temperatures existing in compressed gas bubbles. The main products of the sonolysis of N2O are nitrogen, nitrite and nitrate. N2O enhances the rate of various oxidations such as that of iodide, nitrite and propanol-2. In the methane containing solution, a lot of hydrogen is produced, the main oxidation products being ethane, ethylene, C3- and C4-hydrocarbons and carbon monoxide. A mechanism is postulated which involves both the attack on methane by radicals from the decomposition of water and thermal decomposition of methane. The local radical concentrations are so high that a methane molecule may undergo multiple radical attack. The similarity between sonolytic reactions and reactions occurring in flames is emphasized
Synthese eines Hexadecker-Sandwichkomplexes/Synthesis of a Hexadecker Sandwich Complex
Authors: Kuhlmann Thomas , Siebert Walter
Published: March 2015

Two routes have been studied to obtain the first hexadecker sandwich complexes 4. The reaction between the η3-allyl tetradecker 2b and the cobalt sandwich 3b in refluxing mesitylene leads to red-violet diamagnetic 4bb in 7% yield.

Bis(allyl)nickel and the cyclopentadienylcobalt(2,3-dihydro-1,3-diborol) 3b form the tripledecker η3-allylnickel(μ, η5-dihydro-1,3-diborolyl)-cobalt(η5-cyclopentadienyl) 9b, which reacts at 160 °C with the bis(2,3-dihydro-1,3-diborol)nickel sandwich 10c to give 4bc (21%) and the tetradecker 7b (69%). The constitution of the new complexes is derived from NMR and mass spectra.
Reactions of the Hexafluorothioacetone Dimer with Cyanides of Phosphorus, Arsenic and Germanium
Authors: Roesky Herbert W. , Dhathathreyan Kaveripatnam S. , Noltemeyer Mathias , Sheldrick George M.
Published: March 2015

Cyanides such as P(CN)3 , As(CN)3 , PhP(CN)2 , ButAs(CN)2 and Ge(CN)4 react with [(CF3)2CS]2 (1) by insertion of the carbon atom of the iso-nitrile isomer into the four-membered [CS]2 ring to give compounds PR′3 (2), AsR′3 (3), FP(S)R′2 (4), PhP(S)R′2 (5), ButAsR′2 (6) and GeR′4 (7) respectively, where R′ is the novel heterocyclic ligand[xxx]. The crystal structures of 3 and 7 are reported.
Sandwich-Komplexe mit einem 2,5-Dihydro-1,2,5-thiadiborol-Derivat als Liganden [1] / Sandwich Complexes with a 2,5-Dihydro-1,2,5-thiadiborole Derivative as Ligand [1]
Authors: Siebert Walter , El-Essawi Mohyi El-Din M. , Full Roland , Heck Jurgen
Published: March 2015

Reaction between 3,4-diethyl-2,5-dimethyl-2,5-dihydro-1,2,5-thiadiborol (1, R = CH3) and (C5H5)Co(CO)2 yields the dark red. diamagnetic sandwich [(C5H5)Co(1)] (3, 92%). With [(C5H5)Ni(CO)]2 the green, paramagnetic complex [(C5H5)Ni(l)] (4, 57%) is obtained which at higher temperature forms nickelocene and Ni(1)2. 3 is easily reduced to the radical anion 3T. Neither 3 nor 4 can be stacked to give triple-decker complexes. The ESR spectra of the isoelec- tronic species 3T and 4 are reported.
A Novel Molecular Metal: (Oxamide oximato) (Oxamide oxime)nickel(II). Tetracyanoquinodimethanide, [Ni(oaoH)(oaoH2)]tcnq, and Physical Properties of its Semiconducting Pt Analogue
Authors: Endres Helmut , Bongart August , Nothe Dietrich , Hennig Ingolf , Schweitzer Dieter , Schafer Herbert , Heiberg Hans W. , Flandrois Serge
Published: March 2015

[C4H11N8NiO4]+[C12H4N4]-, Mr = 498.09 is triclinic, P1̄, a = 3.7718(6), b = 7.436(2), c = 17.511(4) Å, α = 88.67(2), β = 86.93(2), γ = 85.05(2)°, V = 488.51 Å3, Z = 1, dc = 1.69 gcm-3, final Rw = 0.035 for 1454 observed independent reflections. The crystals consist of segregated regular parallel stacks of planar metal complex cations and tenq- counterions with intermolecular H bonds stabilizing the structure. The compound is metallic at room temperature. A metal to semiconductor transition around 230 K shows up in thermopower data, in the microwave conduc­tivity and epr around 170 K. It is not visible in the static magnetic susceptibility.
Phosphinsubstituierte Chelatliganden, XIV [1]. Wasserstoff-Brückenbindung in THF-Addukten von Tetracarbonylchrom-und -molybdänkomplexen mit P,S-koordinierten Phosphinothioformamid-Liganden. Kristallstruktur von [(CO)4Cr(PPh2C(S)NHMe)] · THF Phosphine-Substituted Chelate Ligands, XIV [1]. Hydrogen Bonding in THF-Adducts of Tetracarbonylchromium and -molybdenum Complexes with P,S-Coordinated Phosphinothioformamide Ligands. Crystal Structure of [(CO)4Cr(PPh2C(S)NHMe)] · THF
Authors: Kunze Udo , Jawad Hussain , Hiller Wolfgang , Naumer Regina
Published: March 2015

The tetracarbonyl chromium and molybdenum P,S-chelate complexes 1a, b and 2a, b are obtained by low-temperature photolysis of the metal hexacarbonyls with the neutral phosphinothioformamide ligands, Ph2PC(S)NHR (R = Me (a). Ph (b)), as stoichiometric 1/1 IHF adducts. A weak N-H···O(THF) hydrogen bond is deduced from the 1H NMR spectra which show a collapse of the N-methyl doublet in la (Tc -18 °C) but not in 2a. Unusually small P-C(S) couplings are observed in the 13C{1H} NMR spectra. The N-methyl chromium complex la crystal­lizes in the triclinic space group P1 (Z = 2) with the lattice constants a = 1076.6(3), b = 1235.8(3), c = 915.1(3) pm, α = 97.99(4)°, β = 92.73(5)°, γ = 87.63(5)°. The planar thioamide unit adopts the Z configuration and is linked to the tetrahydrofuran molecule by a hydrogen bond (N-H1-O31 164°) with an O···H contact distance of 191 pm.
NMR and Mass Spectroscopic Studies on Catharine
Authors: Atta-ur-Rahman  , Ali Irshad , Chaudhary M. Iqbal
Published: March 2015

The 13C NMR of Catharine is reported. A temperature-dependent study of the 1H NMR of Catharine indicates that it exists as two conformers at room temperature. At higher temperatures, the distinction between the two conformers disappears with the higher rate of equilibration. The mass spectral fragmentation of Catharine as established by link scan measurements is also re­ported.
A Convenient Synthesis of 4-Amino-4-desoxy Sugars
Authors: Malik Abdul , Roosz Michael , Voelter Wolfgang
Published: March 2015

Displacement of the triflyl by the amino group in benzyl-2,3-anhydro-4-triflyl-pyranosides 4-6 gives with inversion the benzyl-2,3-anhydro-4-amino-4-desoxypyranosides 7-9. The triflyl group turns out to be a reactive leaving group which can be replaced by ammonia under mild conditions.
Sodium Dihydrido-bis(2-methoxyethoxo)aluminate (SDMA): Structure and Behaviour in Solutions
Authors: Heřmánek Stanislav , Kříž Otomar , Fusek Jiří , Čásenský Bohuslav , Černý Zbyněk
Published: March 2015

SDMA, according to 27AI NMR almost uniform in benzene, is increasingly disproportionated in the presence of donors in the following order: C6H6 Bu2O ≤ Et2O ≤ anisole < dioxane ≪ THF < monoglyme ≤ diglyme to the NaAlH4-x(OCH2CH2OCH3)x compounds; the structure in solutions is represented by an open-chain oligomer with four-coordinated Na and Al atoms and with Na+ autocomplexed by two bidentate -OCH2CH2OCH3 ligands belonging to two neighbouring Al Atoms.
Cyaninfarbstoffe durch [2+2]-Photocycloaddition substituierter 4-Dimethylamino-α-halogenstilbene / Cyanine Dyes with [2+2]-Photocycloaddition of Substituted 4-Dimethylamino-α-halogenostilbenes
Authors: Pulst M. , Weißenfels M. , Dietz F.
Published: March 2015

The results of the Vilsmeier-Haack-Arnold-reaction with β-4-Dimethylamino-desoxybenzoins are not the expected chloro-formyl-stilbene derivatives but 4-dimethylamino-α-chloro-stilbenes. These compounds undergo a [2+2]photocycloaddition reaction in solid state or fixed on a cellu-lose matrix yielding unstable substituted dichlorotetraphenyl-cyclobutane derivatives, which spontaneously eliminate two molecules of HCl in a following thermal reaction. In this way coloured species - cyanine dyes with a bridged polymethine chain - are formed.