bluuebunny/crossref_metadata_2025 huggingface dataset:
Cyclische Diazastannylene, II1 Intermolekulare Lewis-Säure-Base-Addukte bei 1.3.2.4λ2 -Diazasilastannetidinen / Cyclic Diazastannylenes, II1 Intermolecular Lewis-Acid-Base Adducts of 1, 3,2,4λ 2 -Diazasilastannetidines
Authors: Veith M.
Published: February 2015

1,3-Diorganyl-2,2-dimethyl-I,3,2,4λ2-diazasilastannetidines can be prepared as monomers (organyl = tert-butyl) or dimers (organyl = isopropyl) in nonpolar solvents, depending on the organic nitrogen substituent. The formation of the dimer, which is due to an intermolecular Lewis-acid-base interaction of Sn(II) with nitrogen, can be initiated by solidification. When the tertf-butyl compound is cooled below 0 °C two crystalline modifications are found: a monoclinic phase (C 2/c; a= 10.655(5); b = 24.75(1); c = 17.334(9) Å; β = 106.9(1)°) and a triclinic phase (P1̄; a = 10.68(1); b = 13.51(1); c = 12.36(1) Å; α = 96.2(1); β = 102.6(1); γ = 118.4(1)°). The crystal structures turn out to be built of dimeric and monomeric units in the first case and presumably only dimeric species in the second case. The isopropyl derivative crystallizes in the space group P 21/b (a = 10.77(1); b= 12.14(2); c = 11.15(2) Å; β = 120.2(2)°) with only dimeric units being present, as in the liquid. Interrelationships between the three structures are discussed.
Synthese und 13C-NMR-Spektren tert-butylierter Cyclohexenon-Epoxide Synthesis and 13C NMR Spectra of tert-Butylated Cyclohexenone Epoxides
Authors: Albert Klaus , Schneider Hans-Peter , Koch Dieter , Rieker Anton
Published: February 2015

NMR spectra of several cyclohexenone epoxides obtained by oxygenation of 4-R-2,6-di-tert-butylphenols have been assigned, using substituent induced shifts, offresonance and C - H single-frequency-decoupling techniques, as well as completely C - H coupled spectra. For the -butyl signals the following sequence rules are relevant: methyl carbons and protons = δtBu-C-olefinic(sp2) > δtBu-C-oxirane(sp3) ≥ δtBu-C-OH(sp3); quaternary carbons = δtBu-C-OH(sp3) > δtBu-C-olefinic(sp2) > δtBu-C-oxirane(sp3). In these compounds, the oxirane oxygen causes a highfield shift of the signal of the quaternary C-atom of the feri-butyl group as compared with the influence of a hydroxy group.
Persäureoxidation von Schwefel-Stickstoff-Verbindungen zu Sulfoxiden1 / Oxidation of Sulfur-Nitrogen Compounds to Sulfoxides by Peroxyacids1
Authors: Steudel Ralf , Rose Fritz
Published: February 2015

Trifluoroperoxyacetic acid reacts in 80% yield with (S7N)2S to give colorless crystals of the known (S7N)2SO, and with S7NH to give the formerly unknown unstable hepta-sulfurimide 3-oxide, S7NHO, the properties and vibrational spectra of which are reported.
Neue Silaza-und Silaoxaza-spiro[4.4]nonane und [4.5]decane / Novel Silaza-and Silaoxaza-spiro[4,4]nonanes and [4,5]decanes
Authors: Wannagat Ulrich , Eisele Gerd
Published: February 2015

The formerly unknown spiro systems C-F (Scheme I) with silicon in the spiral center and C, Si, N and O in the framework were synthesized via reactions 2-6 and confirmed in their structure by elemental analysis and spectroscopic data (Table I).
1.1-Dimethyl-1-methoxy-1λ5phospholan und -phosphorinan: Synthese, Struktur und dynamisches Verhalten / 1,1 -Dimethyl-1-methoxy-1λ5 phospholane and -phosphorinane: Synthesis, Structure and Dynamic Behaviour
Authors: Schmidbaur Hubert , Holl Peter
Published: February 2015

The title compounds have been prepared in high yields from equimolar amounts of methanol and the ylides 1-methyl-1-methylene-phospholane and -phosphorinane, respectively. On the basis of a variable temperature 1H, 13C, and 31P NMR study the compounds have been assigned a molecular structure with a pentacovalent phosphorus atom in a trigonal bipyramidal configuration and the methoxy group in an axial position. The molecules are fluxional on the NMR time scale and rapid ligand scrambling is observed at room temperature, predominantly affecting the ring systems. At elevated temperatures an irregular, intermolecular exchange of methoxy groups and CH3P-protons is observed, which is a consequence of a retro cleavage to form ylide and methanol. This process is faster with the phosphorinane than with the phospholane.
Tl6Ag2I10, ein Polyiodid mit Ag2-Paaren Darstellung, Eigenschaften und Kristallstruktur / Tl6Ag2I10, a Polyiodide with Ag2 Pairs Preparation, Properties, and Crystal Structure
Authors: Stoeger W. , Rabenau A.
Published: February 2015

Tl6Ag2I10 forms hexagonal crystals with metallic luster. Under its own I2-pressure the m.p. is 302 °C. In vacuum or under inert gas Tl6Ag2I10 decomposes above 170 °C forming 1 mole of I2. The space group is P6̄2c with the lattice constants a = 10.480 Å, c = 13.415 Å and Z = 2. Tl6Ag2I10 is built up by a framework of Tl6I6 with channels parallel to the c-axis. These channels contain Ag2 pairs with an Ag-Ag distance of 2.98 Å and I4
2- -polyiodide ions, respectively.
The Bimolecular Decay of the α - Hydroxymethylperoxyl Radicals in Aqueous Solution
Authors: Bothe Eberhard , Schulte-Frohlinde Dietrich
Published: February 2015

The bimolecular decay of the hydroxymethylperoxyl radical in aqueous solution (k = 2.1 x 109 M-1s-1) leads mainly (80%) to one molecule of hydrogen peroxid and to two molecules of formic acid.

2 HOCH2OO· → H2O2 + 2 HCOOH

Deuterium kinetic isotope effects show that the decay occurs at room temperature via a short lived (τ < 10-4 s) tetroxid.
CH3NH3SnBrxI3-x (x = 0-3), ein Sn(II)-System mit kubischer Perowskitstruktur / CH3NH3SnBrxI3-x(x = 0-3), a Sn(II)-System with Cubic Perovskite Structure
Authors: Weber Dieter
Published: February 2015

CH3NH3SnBrxl3-x: (x = 0-3) has the cubic perovskite structure with the unit cell parameters a = 5.89 Å (x = 3), a = 6.01 Å (x = 2) and a = 6.24 A (x = 0) and Z = 1. The compounds show intense colour and conducting property. The 119Sn Mössbauer data are consistent with the high symmetry environment of the Sn(II)-ion. A bonding model, using a “p-resonance-bonding”, can explain the properties of the cubic system. The synthesis is described.
Complexes of Oxamic Acid with Al(III), Ga(III), In(III), Tl(III), Y(III), Fe(III), Mn(II) and V(III)
Authors: Kouinis J. K. , Tsangaris J. M. , Galinos A. G.
Published: February 2015

The preparation of complexes of oxamic acid with Al(III), Ga(III), In(III), Tl(III), Y(III), Fe(III), Mn(II) and V(III) is reported. From the study of the infrared and diffuse reflectance spectra and the magnetic moments (for the complexes of Fe(III), Mn(II) and V(III)) it is concluded that in all complexes the metal ion is coordinated with the carboxyl oxygen and the amidic nitrogen, after the ionization of one of the amidic hydrogens.

Octahedral structures are proposed for all the complexes of the trivalent metal ions and the complex K2{Mn(oxamic)2} · 2 H2O.
Bestimmung von Ringstromanisotropieeffekten im 1H-NMR - Spektrum von 9-Phenylderivaten des 1.4-Dimethylanthracens und 1.4-Dimethyltriptycens / Determination of Ring Current Anisotropy Effects in the 1H NMR Spectra of 9-Phenyl Derivatives of 1,4-Dimethylanthracene and 1,4-Dimethyltriptycene
Authors: Eßwein Hans-Dieter , Häfelinger Günter
Published: February 2015

The 1,4-Dimenthyl-9-antliracenyl group is useful as a ring current probe for a 9-phenyl substituent. The splitting between the 1- and 4-methyl group signals due to the diamagnetic ring current anisotropy of the 9-phenylring is 0.84 ppm (0.85 ppm in 9-mesityl- 1,4-dimethylanthracene and 0.86 ppm in 9-phenyl-l,4,6,7-tetramethylanthracene), much larger than in phenylmesitylene (0.32 ppm). In 9-phenyl-1,4-dimethyltriptycene the splitting is reduced to 0.55 ppm due to the change in geometry. By use of an assumed geometric model for all four compounds the magnitude of the splitting could be predicted with a maximum deviation of 0.09 ppm using the tables of Haigh and Mallion. As effective magnetic location for the methyl group the midpoint of the basis of the CH3 cone was chosen. In 9-phenyl-1,4,5,8-tetramethyltriptycene the 9-phenyl ring is not orientated perpendicular but parallel to the 1,8-methyl groups and as the analysis of the ABCX-spin-spin system of the unsubstituted phenyl ring shows tilted by about 24 ° away from the 1,8- methylgroups.
Darstellung und Molekülstruktur von 2-Methylthio-1,3,2-benzodithiastibol / Preparation and X-ray Structure of 2-Methylthio-1,3,2-benzodithiastibole
Authors: Wieber Markus , Burschka Christian , Baudis Ulrich
Published: February 2015

Starting with SbCl3 and 1,2-benzenedithiol, one can easily obtain heterocyclic 2-chloro- 1,3,2-benzodithiastibole [1], which, without isolation, can be treated with a solution of sodium methanethiolate to yield 2-methylthio-1,3,2- benzodithiastibole. Yellow crystals were obtained by recrystallization from acetonitrile. The compound was found to be monomeric in benzene solution.

The crystal structure was solved by means of X-ray diffraction methods and could be refined to an R-value of 0.03 with 870 independent reflections observed. The monoclinic unit cell contains 4 formula units, the space group is P21/c. The structure can be compared with that of 2-methoxi-1,3,2-benzodioxastibole, a preliminary report of which has been given [2]. The compounds are, however, not isomorphous. Interactions between neighbouring molecules in the thiastibole seem to be significantly weaker than in the corresponding oxygen compound.
Eine neuartige Assoziation zwischen Kalium und komplex gebundenem DistickstofF -Struktur von KN2Co(PMe3)3 /A Novel Association of Potassium and Co-ordinated Dinitrogen - Crystal Structure of KN2Co(PMe3)3
Authors: Klein Hans-Friedrich , Hammer Reinhard , Wenninger Josef , Friedrich Peter , Huttner Gottfried
Published: February 2015

[(Me3P)3CoN2]2Mg(THF)4 reacts with potassium metal to give [KN2Co(PMe3)3]6. The same compound is obtained via substitution of olefin in cobaltates K+[Co(olefin)(PMe3)3]- by molecular nitrogen under ambient conditions. Infrared data show that association is preserved even in ether solvents. The stability of cobaltates [Co(PMe3)3L]- increases in the order L = olefin < dinitrogen < PMe3.

Reactions of the title compound proceed as oxidative additions to the monomer with loss of molecular nitrogen. Methyl iodide and allyl bromide yield the fluxional complexes CoCH3(PMe3)4 and η3-C3H5Co(PMe3)3, respectively. Ethyl bromide gives

cis-CoH(C2H4)(PMe3)3 via β-elimination and coordination of ethylene. The molecular structure of [KN2Co(PMe3)3]6 reveals a novel type of cluster: a double cube made up from six KN2 units with six exo-Co(PMe3)3 groups (d(NN) = 116-118 pm, d(CoN) = 170-171 pm).
Tetraisopropylchrom als Ausgangsmalerial zur Synthese von Chromkomplexen /Tetraisopropylchromium as Starting Material for the Synthesis of Chromium Complexes
Authors: Müller Jörn , Holzinger Walter
Published: February 2015

The title compound reacts with σ-donor ligands L (e.g. CO, alkylisocyanides) in THF with formation of CrL6 complexes. From the interaction of Cr(i-C3H7)4 with 1,3-cyclohexadiene no products could be isolated, but with cycloheptatriene in THF (cycloheptadiene)(cycloheptatrienyl)chromium(-I) is produced together with (cycloheptadienyl)-(cycloheptatrienyl)chromium(O). Both complexes may be converted into each other via the cation [C7H9CrC7H7]+ . Reaction of Cr(i-C3H7)4 in THF with 1,3,5-cyclooctatriene yields bis(cyclooctadienyl)chromium(II) and (cyclooctadienyl)(cyclooctatriene)chromium(I) as well as (μ-cyclooctatetraene)bis(cyclooctatriene)dichromium(0) which in solution shows dynamic behaviour similar to tris(cyclooctatetraene)dichromium(0). The products obtained from reactions of Cr(i-C3H7)4 with cyclo-oligo-olefins differ from those formed via the “isopropyl-Grignard synthesis”.
Darstellung, Kristallstruktur und Infrarotspektrum von [MoNCl3 · POCl3]4/Preparation, Crystal Structure and Infrared Spectrum of [MoNCl3 · POCl3]4
Authors: Strähle Joachim , Weiher Ulrich , Dehnicke Kurt
Published: February 2015

[MoNCl3 · POCl3]4 is prepared both by the reaction of MoNCl3 with POCl3 as well as by the reaction of MoCl5 with NCl3 in the presence of POCl3. [MoNCl3 · POCl3]4 crystallizes in the monoclinic space group P21/c with 2 tetrameric molecules in the unit cell. The crystal structure was solved by X-ray diffraction methods (R = 0.033, 1821 observed reflections). The structure consists of planar and almost square Mo4N4-eight-membered rings with alternating Mo-N bond lengths. The distorted octahedral environment of the molybdenum atoms is completed by three terminal Cl-ligands and by the oxygen atom of a POCl3 molecule, which is coordinated trans to the Mo ≡ N triple bond. The IR spectrum is discussed with respect to the vibrational spectra of the isoelectronic niobium complex [NbOCl3 · POCl3]4.
Zur Reaktion von Tris(trifluorvinyl)phosphan mit lithium-organisehen Verbindungen sowie substituierten Lithiumphosphiden / Reactions of Tris(trifluorovinyl)phosphane with Organic Lithium Reagents or Substituted Lithium Phosphides
Authors: Horn Hans-Georg , Kolkmann Friedrich
Published: February 2015

Varius products of the reaction of tris(trifluorovinyl)phosphane with organic lithium reagents have been isolated either while preparing tris(trifluorovinyl)phosphane or by special synthesis. 31P, 19F NMR and mass spectra, although complex, have been used for identification of compounds.
CH3NH3PbX3, ein Pb(II)-System mit kubischer Perowskitstruktur / CH3NH3PbX3, a Pb(II)-System with Cubic Perovskite Structure
Authors: Weber Dieter
Published: February 2015

CH3NH3PbX3 (X = Cl, Br, I) has the cubic perovskite structure with the unit cell parameters a = 5,68 Å (X = Cl), a = 5,92 A (X = Br) and a = 6,27 A (X = I). With exception of CH3NH3PbCl3 the compounds show intense colour, but there is no significant conductivity under normal conditions. The properties of the system are explained by a "p-resonance-bonding". The synthesis is described.
The Structure Model of an Inorganic Ion Exchanger Cobalt(II)-hexacyanoferrate(II)
Authors: Ćeranić T.
Published: February 2015

Cobalt(II)-hexacyanoferrates(II) with incorporated monovalent Na+, K+ , NH4
+ and Cs+ ions have been synthetized. Chemical composition and structure of the unit cell of the crystallites have been determined by X-ray and IR analysis. It has been found that all crystallites containing the monovalent cations are isomorphous having an FCC structure, whereas the cobalt(II)-hexacyanoferrate(II) crystallites tetragonally. In order to explain the properties of these crystallites (which are similar to zeolites) causing their selectivity to monovalent cations, a structure model has been proposed. The values of effective radii of the "cages" and their entrances have been calculated.
Redetermination of the Crystal and Molecular Structure of Cyclohexasulfur, S6 [1]
Authors: Steidel Jürgen , Pickardt Joachim , Steudel Ralf
Published: February 2015

A low temperature (-90 °C) X-ray structural analysis of S6 single crystals yielded improved data for the bond distances (206.8 pm), bond angles (102.6°), and torsion angles (73.8°) of the D3d molecule which are in agreement with current theories of homonuclear sulfur bonds.
Reactions of t-Butyl Peresters, XVIII Peroxyester Reaction of t-Butyl N,N-Dimethylperoxyamidate
Authors: Rawlinson David J. , Konieczny Maria , Sosnovsky George
Published: February 2015

The thermal copper ion catalyzed peroxyester reaction of t-butyl N,N-dimethylperoxyamidate (1, R = N(CH3)2) with cyclohexene results in the formation of the corresponding N,N-dimethylamidate 6 in 20% yield, and 3,3′-dicyclohexenyl (5) in 40% yield. Under

analogous conditions, the reaction of 1, R = N(CH3)2, with tetrahydrofuran gives the corresponding amidate 7 in 6% yield. Only a 2% yield of 6 and no 7 were isolated in the

photochemical variant of the peroxyester reaction. Compound 6 is also obtained in a 12% yield from the reaction of 2-cyclohexen-1-ol (9) with N,N-dimethyl carbamoyl chloride (4) in the presence of pyridine.
Notizen:Ein Bis(perfluorpinakolyl)spirophosphoran/A Bis(perfluoropinacolyl)spirophosphorane
Authors: Röschenthaler Gerd-Volker , Sauerbrey Karl , Schmutzler Reinhard
Published: February 2015

Phenyl-bis(perfluoropinacolyl)phosphorane could be obtained by reacting difluoro-phenyl -perfluoropinacolylphosphorane with dilithium-perfluoropinacolate or by oxidative addition of hexafluoroacetone to phenyl-perfluoropinacolyl-phosphine. The 19F NMR shows nonrigidity of the molecule.
Darstellung und Strukturuntersuchung von Polywolframaten Ein Beitrag zur Aufklärung des Parawolframations A / Preparation and Structure Investigation of Polytungstates A Contribution to the Paratungstate A Problem
Authors: Fuchs Joachim , Flindt Ernst-Peter
Published: February 2015

Polytungstates are obtained by the reaction of hydrated tungsten (VI) oxide with bases or salts after occasional addition of organic solvents. With liquid ammonia the as yet unknown ditungstate, (NH4)2W2O7, is produced. Its IR spectrum has few absorption bands suggesting a very simple constitution. Piperidine yields 5 compounds according to varied experimental conditions, which all exhibit approximately paratungstate compositions but different crystal habits, lattice parameters, solubility and IR spectra. Structure determinations indicate that two of these compounds are heptatungstates, the anion of which, W7O24
6-, has the same structure as the heptamolybdate ion, Mo7O24
6-. From a comparison of their Raman spectra with the spectrum of a freshly acidified sodium tungstate solution (designated as Paratungstate A) it may be concluded that the heptatungstate ion is the predominant species in such a solution. The anion structure of the previously described tributylammonium(5:24):tungstate [(C4H9)3NH]5H3W12O40 was elucidated by X-ray methods. Here the tungsten atoms show the same arrangement as in the α-dodecatungstatophosphate ion (Keggin structure).
Beiträge zur Chemie des Schwefels, 116 [1]Kristall-und Molekülstrukturen von 1.2.4.5-Benzotetrathiepin und 3-Methyl-1.2.4.5-benzotetrathiepin / Contributions to the Chemistry of Sulfur, 116 [1]Crystal and Molecular Structures of 1,2,4,5-Benzotetrathiepine and 3-Methyl-1,2,4,5-benzotetrathiepine
Authors: Fehér F. , Engelen B.
Published: February 2015

The structures of 1,2,4,5-benzotetrathiepine and 3-methyl-1,2,4,5-benzotetrathiepine were determined by X-ray structure analysis. The constitution of the molecules, which was proposed by way of spectroscopic data, could be verified. The conformation of the seven-membered rings is the chair form. The position of the methyl group in 3-methyl-1,2,4,5-benzotetrathiepine is equatorial with respect to the seven-membered ring. Details of the conformations are discussed. Bond distances and angles are compared with those in other molecules, which have similar structures.
Complexes of Cu(II) and Ni(II) with N, N′-(Dipicolyl) 1,8-naphthylenediamine
Authors: Tsangaris J. M. , Perlepes S. , Galinos A . G.
Published: February 2015

The preparation of the new compound N,N′-(dipicolyl)1,8-naphthylenediamine = DPNAP is reported which can serve as a tetradentate ligand.

Complexes of DPNAP with Cu(II) and Ni(II) were prepared and their IR , visible UV spectra and magnetic moments were investigated.
Solvolytic Studies on Methylnorbornyl Systems: Investigations on the Synthesis of 2-Exo-methyl-6-norbomylideneacetic Acid
Authors: Radhakrishnan J.
Published: February 2015

3-Nortricyclyl bromide (11) was transformed in four steps to norbornan-3,6-dione (10). Methyl 4-hydroxy-2-butynoate (19) was prepared from propargyl alcohol and its alkylation reactions with 3-methylcyclopentanone investigated. Methyl 4,4,5-triethoxycarbonylpentanoate (22) was obtained by the sequential alkylation of diethyl malonate with ethyl bromoacetate and methyl acrylate, and its base catalysed cyclization studied. Cyclopentadiene was converted to 2-exo-methylnorbornan-6-one (17) in eleven steps.
Trimethylzinnazid und Trimethylzinnazid · Trimethylzinnhydroxid / Trimethyltin Azide and Trimethyltin Azide-Hydroxide
Authors: Müller Joachim
Published: February 2015

(CH3)3SnN3 (1) and (CH3)3SnN3 · (CH3)3SnOH (2) were characterized by physical and spectroscopic properties. In solution the azido groups show a temperature dependent site exchange.
Notizen: Elektrochemie von Übergangsmetall-π-Komplexen, III. Olefin-und Aromatenkomplexe des Chroms / Electrochemistry of Transition Metall-π-Complexes, III. Olefinic and Aromatic Sandwich Complexes of Chromium
Authors: Koelle Ulrich , Holzinger Walter , Müller Jörn
Published: February 2015

Olefinic and aromatic sandwich-complexes of chromium have been oxidized and reduced electrochemically. Oxidation in dichloromethane at a Pt electrode was found to be in most cases chemically reversible. The oxidation of complexes with an 18-electron configuration was observed in a potential range of E1/2 = -0.65 to -0.8 V whereas oxidation of complexes with a 17-electron configuration occurs between E1/2 = -0.2 and -0.4 V. Only one of the 18- electron complexes but all 17-electron complexes were reduced in THF, most of these electron transitions being chemically reversible.
Alkinylverbindungen von Übergangsmetallen, XXXVI [1]. Kupfer(I)-Verbindungen des 1.2-Diethinylbenzols / Alkynyl Compounds of Transition Metals, XXXVI [1]. Copper(I) Compounds of 1,2-Diethynylbenzene
Authors: Nast Reinhard , Lepel Wulf-Heiner
Published: February 2015

The diamagnetic complexes 1,2-C6H4(C≡CCu)2, 1,2-C6H4(C≡CCU)2·2 Pet3, 1,2-C6H4(C≡CCu)2·Pet3 (et=C2H5) and K3Cu(1,2-C6H4(C≡C)2)2 are prepared by reactions of Cul with the dipotassium salt of 1,2-diethynylbenzene o-C6H4(C≡CK)2 in liquid ammonia. The IR-active νC≡C frequencies and possible structures of the polymeric solids are discussed.
Kristall- und Molekülstruktur des dimeren (Tetramethylcyclobutadien)dibromo-nickel(II) / Crystal and Molecular Structure of the Dimeric (Tetramethylcyclobutadiene)dibromo-nickel(II)
Authors: Thewalt Ulf , Hemmer Reinhard , Brune Hans Albert
Published: February 2015

The title compound, A, has been prepared from the corresponding chloro complex by reaction with potassium bromide in aqueous solution. A crystallizes in the monoclinic space group P21/n with Z = 2 and lattice parameters a = 11.748(5), b = 10.419(4), c = 8.383(4) Å and β = 95.35(5)°. An X-ray analysis shows that A posseses crystallographic symmetry 1̄, that within the limits of error, the π-bonded cyclobutadiene ring is a square with an average C-C bond distance of 1.464 Å, and that the methyl groups are displaced away from the nickel atom, the average distance between the ring plane and the methyl C atoms being 0.20 Å.
Salts of Ferricinium Cation and its Homologues: NMR Investigation, I On Mechanisms of Spin Derealization in Salts of Ferricinium and 1,1′-Dimethylferricinium Cation
Authors: Lyatifov U'tifat R. , Solodovnikov Stanislav P. , Babin Valery N. , Materikova Rosa B.
Published: February 2015

1H and 13C NMR spectra of hexafluorophosphates of ferricinium (1) and 1,1′-dimethyl -ferricinium cations (2) and the EPR spectrum of 2 were recorded. Pseudocontact and contact contributions of isotropic shift were calculated and constants of hyperfine inter-action estimated according to Jesson. It is shown that the calculations of pseudocontact and contact shift via magnetic susceptibility components according to Kurland and McGarvey do not change the signs of HFS constants. According to the suggested mecha-nisms of spin derealization the π-contribution is the dominating one.
Dimethylhalonium-Ionen in Aluminiumhalogenid/Methylhalogenid-Lösungen / Dimethylhalonium-Ions in Aluminium Halide/Methyl Halide Solutions
Authors: Brüggeller Peter , Mayer Erwin
Published: February 2015

Evidence for the formation of (CH3)2Br+ and (CH3)2I+ in CH3Br and CH3I solutions saturated with AlBr3 comes from the appearance of a second singlet in the 1H NMR spectrum. The (CH3)2Br+ ion is formed at -40 °C to about 5 mol%, the (CH3)2I+ ion at -12 °C with 50 mol% yield. At higher temperatures the concentration of the halonium ions decreases rapidly. The (CH3)2Br+ ion is not detectable at room temperature, the concentration of (CH3)2I+ decreases to about 30 mol%. Dilution of the saturated solutions with methyl halide also reduces the halonium ion concentration. An AlBr3/CH3Br solution with a molar ratio of 1:3 at -40 °C shows no sign of (CH3)2Br+ formation in the XH NMR spectrum. Both effects are best explained by formation of dimethylhalonium ions from the adduct CH3X-AIX3 and by dependence of adduct concentration on temperature and dilution. Exchange of (CH3)2Br+ and (CH3)2I+ with methyl halide is slow on the NMR time scale at low temperatures similar to the results in SbF5/SO2. The 1H NMR singlets of (CH3)2Br+ and (CH3)2I+ are shifted to lower field by 1.32 and 1.68 ppm in comparison with the chemical shifts in SbF5/SO2 solution
Untersuchungen an quartären Pyridiniumsalzen, IX [1] Pyridiniumsalze mit Amidingruppe. Darstellung und Reaktion mit Base / Investigations of Quaternary Pyridinium Salts, IX [1] Pyridinium Salts with Amidine Group. Preparation and Reaction with Base
Authors: Gündel Wolf-Hellmut
Published: February 2015

3-Pyridinecarboximidamide gave with alkylating agents quaternary salts (2), that rearrange on addition of anionic base to 2-amino-pyridinecarbaldehyde (3). Derivatives of 3 can be obtained by reaction of 3-cyano-pyridinium salts with primary amine on addition of anionic bases
Die Kristallstruktur der Salze K2Au2I6 und Cs2AgxAuI
1-xAuIIIBr6. Ein Beitrag zur Kristallchemie der Alkalihexahalogenoaurate(I,III) / Crystal Structure of the Salts K2Au2I6 and Cs2AgxAuI
1-xAuIIIBr6. A Contribution to the Crystal Chemistry of the Alkali Hexahalogeno Aurates(I,III)
Authors: Strähle Joachim , Gelinek Jürgen , Kölmel Marianne , Nemecek Anna-Maria
Published: February 2015

K2Au2l6 crystallizes in the monoclinic space group P21/n. It is built up by linear anions AUI2-, square-planar anions AUI4-, and K+ cations. The coordination of the gold(I) and gold(III) atoms is completed by additional iodine atoms at larger distances to form compressed and elongated octahedra, respectively. Like the other known alkali hexahalogeno aurates(I,III), K2AU2I6 belongs to a family of topologically related structures in which the perovskite is the aristotype. The actual structures depend on the size of the alkali metals: more dense structures with smaller coordination numbers for the smaller alkali metals result from a rotation of the coordination octahedra of the gold atoms. Cs2AgAuBr6 does not crystallize in the ideal cubic perovskite structure, as was described in 1942, but a disordered cubic phase (a = 550.1 pm, space group Pm3m), with the composition Cs2AgxAuI1-xAuIIIBr6 (x ≈0.25), can be prepared from HBr solution. Its cubic symmetry is the result of a statistical superposition of the coordination polyhedra of AgI, AuI and AuIII
Zur Verbindungsbildung von MeO : M2O3, Teil III Zur Kenntnis von BeGa2O4 / Compound Formation MeO : M2O3, Part III BeGa2O4
Authors: Schweizer M. , Müller-Buschbaum Hk.
Published: February 2015

A new compound, BeGa2O4, was prepared by high temperature reaction between BeO and Ga2O3. X-ray single crystal investigations show a hitherto unknown structure type of M2+M2
3+O4 compounds. BeGa2O4 crystallizes with hexagonal symmetry a = 775.0 and c = 298.0 pm, space group C2
6h-P63/m. Be2+ and Ga3+ are statistically distributed and are surrounded by O2--tetrahedra
Röntgenographische und IR-Spektroskopische Untersuchung der Substitution von Phosphat- durch Sulfat-Ionen im Fluorapatit-Gitter / X-rayand IR Spectroscopic Investigation of the Phosphate Substitution by Sulfate Ions in the Fluoroapatite Lattice
Authors: Apella Maria C. , Baran Enrique J.
Published: February 2015

Phases of composition Ca10-z;Naz(PO4)6-z;(SC)4)xF2, obtained during the substitution of PO4
3- by SO4
2- ions in the Ca10(PO4)6F2 lattice have been investigated by means of X-ray and IR spectroscopic methods. The stepwise introduction of SO42- ions produces an increasing distorsion of the lattice, although the parameters of the "pseudo-hexagonal" unit cell are practically invariant. The not well defined IR spectra are greatly dependent of the oxoanion present in largest concentration
Darstellung und Kristallstruktur von Ca9Mn4Bi9 und Ca9Zn4Bi9 /Preparation and Crystal Structure of Ca9Mn4Bi9 and Ca9Zn4Bi9
Authors: Brechtel Erwin , Cordier Gerhard , Schafer Herbert
Published: February 2015

The new compounds Ca9Mn4Bi9 and Ca9Zn4Bi9 crystallize in the orthorhombic system (Pbam) with

Ca9Mn4Bi9: a = 2242 ± 2 pm, b = 1256 ± 1 pm, c = 472 ± 1 pm,

Ca9Zn4Bi9: a = 2212 ± 2 pm, b = 1264 ± 1 pm, c = 465 ± 1 pm.

In the structure of the isotypic compounds there are Mn(Zn)Bi4-tetrahedra connected to chains by common corners. Four of these chains are connected by common comers to „Einervierfachketten“ in Liebau’s nomenclature for inosilicates.
Ion Exchange Equilibria of Cobalt(II)-M-hexacyanoferrates(II) with K, NH4 and Cs
Authors: Ćeranić T. S. , Adamović R.
Published: February 2015

The inorganic ion exchanger cobalt(II)-M-hexacyanoferrate(II), M = K, NH4 and Cs, and its selectivity for the alkali metal ions are defined by their isotherms at three different temperatures and by the calculated thermodynamic functions ΔG°, ΔH° and ΔS°. The thermodynamic data are discussed on the basis of the radii of competing ions as well as on the steric limitations of the ion exchanger phase, i.e., the thermodynamic magnitudes which control the selectivity of those ion exchangers.
Synthese von Derivaten des 1-Adamantylbenzols /Synthesis of Derivatives of 1-Adamantylbenzene
Authors: WeiB Jörn-Volker , Wray Victor , Schmutzler Reinhard
Published: February 2015

p-Di(1-adamantyl)benzene (6a), a mixture of the m- and p-isomers of 1-adamantyl-toluene (6b), and p-(l-adamantyl)bromobenzene (6c) were obtained in a Friedel-Crafts type reaction from 1-adamantyl fluoride and benzene, toluene, bromobenzene, respectively, in the presence of the Lewis acid phenyltetrafluorophosphorane. Characterisation of the products -all previously described in the literature -was by analysis and 13C NMR spectroscopy.
Photodimerisation of Amidopyrine [1,2] An Example of [2+2] Photocycloaddition of an Enamine-Like Structure
Authors: Reisch J. , Abdel-Khalek M.
Published: February 2015

The photochemical behaviour of amidopyrine (1) in cyclohexane was studied. The photodimer (2) and three fragmentation products (3-5) could be isolated and identified with the help of spectroscopic methods. The participation of 4-pyrazolin-3-ones in photochemical cycloadditions is demonstrated for the first time.
XPS Spectra of Spin-Triplet Cobalt(III) Complexes
Authors: Brown Dennis G. , Weser Ulrich
Published: February 2015

The X-ray photoelectron spectra of cobalt(III) complexes in an unusual spin triplet state are reported. The binding energies in the 2P spectral region are somewhat low and the spectra exhibit rather strong satellite structure. The Co 2P1/2-CO 2P3/2 separations and satellite intensities appear to be related to the magnetic moments of the complexes as has been suggested previously for cobalt(II) compounds.
Redoxreaktion zwischen Chinolinium-Salzen und Alkoholaten / Redoxreaction between Quinolinium Salts and Alcoholates
Authors: Gündel Wolf-H. , Berenbold Helmut
Published: February 2015

Quinolinium Salts, Redox Reactions Quaternary salts of 3-quinolinecarboxamide and 3-quinolinecarbonitrile react after addition of ZnCl2 with ethanol (or 2-propanol) to the corresponding 1,4-dihydroquinoline and ethanol (or propanone). This hydride transfer can be achieved with aluminium-triisopropoxide, too. Lipophilic insertionproducts (4,5,7,8) react with ethanol (or 2-propanal) after ZnCl2 addition to quinolinium-alcoxides, and then to the 1,4-dihydro-quinoline and ethanal (or propanone).
Ein Beitrag zur Chemie von Verbindungen des Bautyps MxPd3O4 / A Contribution to the Chemistry of the Compounds MxPd3O4
Authors: Meyer H.-J. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of a new compound Pd0.5Pd3O4 were prepared and investigated by X-ray methods. It crystallizes with NaxPt3O4-type structure (space group Oh
3-Pm3n, a = 575.6 pm). The distribution of the oxydation states of Pd with respect to the lattice positions is discussed.
Synthese und Reaktionen von Phosphonio-acetyl-Peptiden und ihren Yliden / Synthesis and Reactions of Phosphonio-acetyl Peptides and Ylides
Authors: Kunz Horst , Kauth Hermann
Published: February 2015

Triphenylphosphonio-acetyl-(Tpa)-amino acids (5) and peptide esters (6) are prepared from the corresponding monpchloro acetyl derivatives (3) and (4). Alternatively the Tpa- amino acids (5) may be obtained by treatment of the N-silyl amino acid silylesters with the triphenylphosphonio-acetic acid phenylester (7) or the corresponding ylide (8). Tpa- amino acids prepared in this manner may be used for peptide condensation. The Tpa- group is acid-stable. In aprotic media the ylides of the Tpa-dipeptide esters (13) are formed on treatment with strong bases, and are converted in the course of the Wittig- olefination to the substituted acrylo peptide esters 15. The trans o-nitro-cinnamoyl moiety may be cleaved from the amino function of the peptide esters as 3,4-dihydro-a- quinolone via catalytic hydrogenation.
Notizen: Sr3Al2Sn2 und Ba3Al2Sn2 - ternäre Stannide im Ta3B4-Strukturtyp / Sr3Al2Sn2 and Ba3Al2Sn2 - Ternary Stannides in the Ta3B4-Structure
Authors: Widera Axel , Schäfer Herbert
Published: February 2015

The new compounds Sr3Al2Sn2 and Ba3Al2Sn2 crystallize in the orthorhombic system (Immm-D2h
25) with

Sr3Al2Sn2: a = 446.5 ± 1 pm,

b = 1979.5 ± 2 pm,

c = 494.4 ± 1 pm,

Ba3Al2Sn2: a = 459.4 ± 1 pm,

b = 2063.4 ± 2 pm,

c = 523.0 ± 1 pm,

and build up an ordered variant of the Ta3B4- structure type.
Fluorescein-photosensitized Furan Oxidation in Methanolic and Reversed Micellar Solutions, Part II Kinetic Analysis
Authors: Miyoshi Norio , Tomita Giiti
Published: February 2015

The 1,3-diphenylisobenzofuran oxidation was investigated in methanolic and dodecyl-ammonium propionate reversed micellar solutions using fluorescein sodium as photosensitizer. The furan oxidation was caused by the singlet oxygen mechanism (Type II). Aniline enhanced remarkably the furan oxidation in methanolic solutions, but inhibited highly this oxidation in the reversed micellar solutions. This enhancement of the furan oxidation was considered to be brought about by the occurrence of a radical mechanism (Type I) besides Type II mechanism. No Type I reaction occurred in the micellar solutions. The rate constants concerning with both reaction processes were evaluated by kinetic analysis, employing various aryl-and alkyl-amines. The reaction mechanism of Type I and the quenching mechanism of singlet oxygen by amines were discussed from the relationship between the rate constants, and the ionization potential of amines and the solvent polarity.
Photomineralisierung chlorierter Alkane, Alkene und Aromaten an Kieselgel / Photomineralization of Chlorinated Alkanes, Alkenes and Aromatics on Silica Gel
Authors: Schmitzer J. , Gäb S. , Bahadir M. , Körte F.
Published: February 2015

The photodegradation to CO2 (photomineralization) of chlorinated alkanes, alkenes and aromatics adsorbed on silica gel was examined. In addition to CO2, Cl- and Cl2 were determined. The degradation depends considerably on the activity of the surface and decreases in the order alkenes > alkanes > aromatics.
Die Kristall- und Molekülstruktur zweier spirocyclischer Diazadiphosphetidine / The Crystal and Molecular Structure of Two Spirocyclic Diazadiphosphetidines
Authors: Lux Dieter , Schwarz Wolfgang , Hess Heinz , Zeiß Werner
Published: February 2015

The crystal structure of the two spirocyclic diazadiphosphetidines (Me2C2O2)(Me2N)2P2N2(SiMe3)2 (1) and (Me2C2O2)2(Me2N)2P2N2(SiMe3)2 (2) were determined. In both compounds the dimethylamino groups are arranged in a cisposition with respect to the plane of the four-membered ring. There are no unusually long PN distances in the four-membered ring of 2, although 2 monomerizes easily and quantitatively at room temperature to give 3.
Beiträge zur Chemie des Silieiums und Germaniums, XXIX [1] 29Si-NMR-spektroskopische Untersuchungen von geradkettigen und verzweigten Silanen / Contributions to the Chemistry of Silicon and Germanium, XXIX [1] 29Si NMR Spectroscopic Investigations on Straight and Branched Silanes
Authors: Hahn Josef
Published: February 2015

,

The structure of the straight silanes SinH2n+2 (1 ≤ n ≤ 7) and of the branched isomers isotetrasilane, iso- and neopentasilane, 2-silyl- and 3-silylpentasilane, 2,3-disilyltetrasilane as well as 2-silyl- and 3-silylhexasilane could be unambiguously elucidated by 29Si NMR spectroscopy. Systematic trends in the chemical shift and coupling parameters were observed and an empirical relationship between δ(29Si) of a 29Si nucleus and the number of the neighbouring silicon atoms in αβor γposition is given. In 1H decoupled spectra the nuclear Overhauser effect on the 29Si resonance was found to increase with increasing distance of the 29Si nucleus from the end of the chain. A complete analysis of the multi spin systems of disilane, trisilane and isotetrasilane was performed and the signs of the 29Si,H- and H,H-long range coupling constants were determined with regard to the negative sign of 1J(29SiH).
Beiträge zur Chemie der Pyrrolpigmente, XXXVI [1] Zur anaeroben Photochemie von 21.24 - Diinethy 1 - aetiobiIi verdin -IV -γ / On the Chemistry of Pyrrole Pigments, XXXVI [1] On the Anaerobic Photochemistry of 21,24-Dimethyl-aetiobiliverdin-IV -γ
Authors: Falk Heinz , Thirring Klaus
Published: February 2015

21,24-Dimithylaetiobiliverdin-IV-γ was prepared via excessive methylation of aetiobili. verdin-IV-γ. Its configuration could be established using 1H NMR methods. Photoisomerisation yields the (E,Z,Z) and (E,Z,E) diastereomers which means that the selectivity observed in photoisomerisation of bilatrienes-abc can be removed by making the ligands of the lactame moiety adjacent to exocyclic double bonds nearly equal. The torsional angles at the methine single bonds are approximatly equal in the three diastereomers resulting in much the same UV-VIS spectra. The obviously strong distortion of the conjugated chromophor allows for the deceleration of certain radiationless deexcitation paths thereby allowing for photoisomerisations in homogenous solution.
Der Aufbau von Nd2NiO4 und seine Verwandtschaft zu La2NiO4 und La2CuO4 / The Structure of Nd2NiO4 and its Relationship to La2NiO4 and La2CuO4
Authors: Lehmann U. , Buschbaum Hk. Müller-
Published: February 2015

Single crystals of Nd2NiO4 were prepared by plasma and CO2-LASER technique and analysed by X-ray single crystal methods. Nd2NiO4 is the first compound of the orthorhombically dis-torted La2CuO4-type.
Elektrochemische Synthesen, II [1]. Theoretische Aspekte der elektrochemischen Synthese von Komplexen / Electrochemical Syntheses, II [1]. Theoretical Aspects of the Electrochemical Synthesis of Complexes
Authors: Grobe Joseph , Keil Michael , Schneider Bernd , Zimmermann Heinz
Published: February 2015

A theoretical model for the electrochemical synthesis of transition metal complexes in low oxidation states has been developed on the basis of Pearson’s HSAB concept. A MO description is used to discuss the important practical implications of the model.
Electronic Effects of Aryl and Heteroaryl Groups on the Rate of Nucleophilic Displacement of Chlorine from 5-Heteroaryl(or Aryl)-2-chloropyrimidines by Piperidine
Authors: Allen David W. , Buckland David J. , Hutley Barrie G.
Published: February 2015

The kinetics of nucleophilic displacement of chlorine from a series of 2-chloro-5-heteroaryl( or aryl)pyrimidines by piperidine have been studied in order to assess the electronic effects of the 5-substituent. The observed order of reactivity is 5-(1-methylpyrrol-2-yl) < 5-p-anisyl < 5-p-tolyl < 5-phenyl < 5-(2-thienyl) < 5-(2-furyl) < 5-(m-chlorophenyl). The reactions are enthalpy-controlled and the rate data can be explained as a consequence of the electron-withdrawing or electron-donating ability of the 5-substituent. Synthetic routes to the compounds studied are also described.
Towards a Classification of Singlet Carbenes
Authors: Schoeller Wolfgang W. , Brinker H.
Published: February 2015

According to one-electron perturbation theory singlet carbenes can be classified as (a) electrophilic, (b) nucleophilic or (c) ambiphilic in their addition properties towards olefines. The nucleophilicity of the σ-orbital in :CX1X2 should increase with decreasing electronegativity of X1 (X2).
Elektrochemische Synthesen, III [1] Metallcarbonyle und Phosphan-Derivate der Elemente der Gruppe VI B / Electrochemical Syntheses, III [1] Metal Carbonyls and Phosphane Derivatives of Group VI B Elements
Authors: Grobe Joseph , Zimmermann Heinz
Published: February 2015

The electrochemical synthesis of group VI B metal carbonyls and phosphane derivatives thereof from suitable metal complexes of oxidation state +III (acetylacetonates, chloropyridin compounds) and from metal anodes is described.
Organobleiverbindungen von Mercaptocarbonsäuren / Organolead Compounds of Mercaptocarboxylic Acids
Authors: Hager Claus-Dierk , Huber Friedo
Published: February 2015

Phenyllead Compounds, Methyllead Compounds, Organolead-S-mercaptocarboxylic Acids Triphenyl-and diphenyllead derivatives of mercaptocarboxylic acids (H2Mc) with general formulas Ph3Pb(HMc), (Ph3Pb)2Mc, Ph2Pb(HMc)2 and R2Pb(Mc) (R = Ph, Me) have been prepared by gentle reaction of H2Mc with Ph3PbOH, (Ph2PbO)n or Me2Pb(OH)2 in CHC13. According to spectroscopic data the ligand in all compounds is bound to Pb through S. Ph3Pb(HMc) (HMc = SCH2COOH, SCH2CH2COOH, SCH(CH3)COOH, SCH(COOH)CH2COOH forms dimers in the solid state and in CC14, Ph2Pb(CH2CH2COOH)2 forms polymers via H-bonded COOH groups. Ph3Pb(o-SC6H4COOH) is monomeric. For R2Pb(Mc) polymeric structures are proposed. Me3PbOH and H2Mc react to give an inter-mediate, which disproportionates to give Me2Pb(Mc) (Mc = SCH2COO, SCH2CH2COO) and Me4Pb.
Dicarbonyl-, Carbamoyl-carbonyl-und Carbomethoxo-carbonyl-Komplexe des Rhodiums mit tri-und tetratertiären Phosphinliganden [1] Dicarbonyl-, Carbamoyl-carbonyl-and Carbomethoxo-carbonyl Complexes of Rhodium with Tri-and Tetratertiary Phosphine Ligands [1]
Authors: Behrens Helmut , Ellermann Jochen , Hohenberger Ewald F.
Published: February 2015

The cationic dicarbonyl complexes [Rh(CO)2(R2PCH2)3CRʹ]PF6 (R = C6H5; Rʹ = CH3, -CH2PR2), formed by high pressure synthesis from RhCl3(H2O)3, CO and (R2PCH2)3CRʹ react with liquid ammonia at 20 °C to give the carbamoyl complexes Rh(CO)(CONH2)(R2PCH2)3CRʹ. At 100 °C in liquid ammonia the carbamoyl-carbonyl complexes Rh(CO)(CONH2)(R2PCH2)3CRʹ form the CO-bridged, dinuclear compounds (μ-CO)2[Rh(R2PCH2)3CRʹ]2. Upon treatment of Rh(CO)(CONH2)(R2PCH2)3CRʹ with CH3OH the carbomethoxo carbonyl complexes Rh(CO)(COOCH3)(R2PCH2)3CRʹ are obtained. The new compounds were characterised, as far as possible, by their IR, Raman and 31P NMR spectra.
Reinvestigation of the Behaviour of Benzal-anils towards the Action of Potassium Cyanide
Authors: Gawad Ibrahim I. Abd El , Harhash Abd El-Hammid , Mohamad  , El-Zahab M. M. Abou
Published: February 2015

Reinvestigation of the behaviour of benzal-anils (1) towards the action of potassium cyanide was found to give a mixture of 4-imidazolidinone (6) and 4-imidazolone (7). 6 was also obtained by benzaldehyde addition to α-arylamino-α-phenylacetonitrile (7) or by condensation of benzaldehyde with α-phenylamino-α-phenylacetamide (8). The partial conversion of 6 and 7 to each other was discussed.
Reduktone von Tetram-, Tetron- und Thiotetronsäuren/Reductones of Tetramic, Tetronic and Thiotetronic Acids
Authors: Stachel Hans-Dietrich , Poschenrieder Hermann , Burghard Hans
Published: February 2015

The 3-spiro-3ʹ,3ʹ-dimethyl-2ʹ-oxiranes of 5-benzylidene-2,4-dioxo-pyrrolidone, 5-benzyl-idene-2,4-dioxotetrahydrofuranone and 5-benzylidene-2,4-dioxotetrahydrothiophene yield the corresponding heterocyclic reductones (3 a-c) upon treatment with sulfuric acid. The tetramic acid reducton 3a can also be obtained by hydrolysis of the diazoniumsalt 5.
Darstellung und Charakterisierung von 1.4- und 1.5-Dienkomplexen des Platins- Röntgenstrukturanalyse von Dichloro-2.5-diphenyl-1.5-hexadienplatin(II), Cl2Pt((C6H5)2C6H8) / Preparation and Characterization of 1,4- and 1,5-Diene Complexes of Platinum; X-ray Analysis of Dichloro-2,5-diphenyl-1,5-hexadiene Platinum(II), ((Cl2Pt(C6H5)2C6H8)
Authors: Kopp Michael , Krauth Luise R. , Ratka Richard , Weidenhammer Klaus , Ziegler Manfred L.
Published: February 2015

The reaction of cis-(C6H5CN)2PtCl2 and Na2PtCl4 with the dienes 1,4-pentadiene and 2,5-diphenyl-1,5-hexadiene yields the species cis-(1,4-pentadiene) PtCl2 and cis-(2,5-diphenyl-1,5-hexadiene)PtCl2, respectively. The compounds have been fully characterized by elemental analysis, IR, 1H-NMR, mass spectroscopy and by X-ray methods
Methylenverbindungen von Nichtmetallen, III [1]. Metallcarbonyl-Komplexe mit methylenverbrückten Diphosphor-Liganden / Methylene Compounds of Non-Metals, III [1] Metal Carbonyl Complexes of Methylene-Bridged Diphosphorus Ligands
Authors: Fild Manfred , Handke Wolfgang , Sheldrick William S.
Published: February 2015

Compounds of the type R2PCH2PR2 (R = PriO, Me2N) react with cis-LM(CO)4 (L = Bicyclo[2,2,1]hepta-2,5-dien; M = Cr, Mo, W) complexes to yield cis-substituted [R2PCH2PR2]M(CO)4 derivatives. The structure of the molybdenum compound, [(PriO)2PCH2P(OPri)2]Mo(CO)4, has been determined. Diphosphorus ligands of the type R2P(S)CH2PR2 (R = F, PriO) are monodentate and form [R2P(S)CH2PR2]2Mo(CO)4 complexes, whereas the compound (Me2N)2P(S)CH2P(NMe2)2 acts as a bidentate ligand
An Electronegativity Scale for RSO2 Groups as Empirically Estimated from the S-Cl Bond Lengths of Sulphonyl Chloride Molecules
Authors: Hargittai Istvan , Bliefert Claus
Published: February 2015

Electronegativities for some RSO2 groups have been estimated from the S-Cl bond lengths of sulfonic acid chlorides by use of the Schomaker- Stevenson equation.
Neue Untersuchungen zur Herstellung von Chlornitrat ClONO2 [1] / New Methods for the Preparation of Chlorine Nitrate ClONO2 [1]
Authors: Schmeißer Martin , Eckermann Werner , Gundlach Klaus Peter , Naumann Dieter
Published: February 2015

ClONO2 can be prepared in good yields from the reactions of anhydrous metal nitrates M(NO3)2 (M = Ca, Sr, Pb) with ClF as well as from the direct reaction of Cl2, HgO and N2O5.
Anwendung der 11B-NMR-Spektroskopie zur Untersuchung von Hydroborierungen, IHydroborierung von 3-Methyl-1.3-butadien mit Boran in Tetrahydrofuran und Dimethylsulfid / Application of 11B NMR Spectroscopy to the Study of Hydroboration, I Hydroboration of 3-Methyl-1,3-butadiene with Borane in Tetrahydrofurane and Dimethyl Sulfide
Authors: Contreras Rosalinda , Wrackmeyer Bernd
Published: February 2015

The intermediacy of 3-methyl-1-boracyclopentane in the hydroboration of 3-methyl-1,3-butadiene with borane in tetrahydrofurane (BH3-THF) and dimethyl sulfide (BH3-DMS) has been established by means of 11B NMR spectroscopy. The reaction proceeds through the trialkylborane stage (3:2 products) and the latter undergo exchange reactions with boron hydrogen compounds present. This has been proved independently by studying the 11B NMR spectra of the mixtures between the 3:2 products and BH3-THF and BH3-DMS, respectively. Evidence is provided that opening of the boracyclopentane ring in exchange reactions is accompanied by exocyclic exchange. These results are further confirmed by the 11B NMR spectra of the mixtures between 1-phenyl-3-methyl-1-boracyclopentane and BH3-THF and BH3-DMS, respectively. 11B NMR spectra of the 3:2 products dissolved in DMS allow evaluation of the isomer distribution.
Compounds of Complex Halo and Pseudohalo Acids of the Group II B Metals, Part II [1]Etherate and Aniline Compunds of Cd(II)
Authors: Perlepes S. P. , Zafiropoulos Th. F. , Kouinis J. K. , Galinos A. G.
Published: February 2015

The preparation of new etherate and aniline compounds of the mixed complex halo-acids HCdCl2I and H2CdI2Cl2 is reported.

Analytical, conductometric, spectral (UV and IR) and data from X-ray powder spectra were used for the characterization of the complexes. The structure of the aniline complexes, in the solid state, cannot be deduced with certainty.