bluuebunny/crossref_metadata_2025 huggingface dataset:
Osmiumisonitril-Komplexe mit Os-H-, Os-CH3- und Os-Au-Bindungen [1] / Osmiumisonitrile Complexes Containing Os-H. Os-CH3 and Os-Au Bonds [1]
Authors: Werner H. , Weinand R.
Published: February 2015

The complexes C6H6Os(PMe3)CNR (R = Me, t-Bu, p-Tol, Ph) are prepared from [C6H6OsI(PMe3)CNR]PF6 and NaC10H8. They behave as metal bases and react with NH4PF6, CH3I and ClAuPPh3 to form salts of the corresponding cations [C6H6OsX(PMe3)CNR]+ where X is H, CH3 and AuPPh3, respectively. The reactions of [C6H6OsX(PMe3)CNR]PF6 (X = I, H, CH3) with excess PMe3 lead to displacement of the benzene ring and formation of the complexes trans-[OsX(CNR)(PMe3)4]PF6.
Synthese und Kristallstruktur eines polymeren Addukts von 2.2′ -Dipyridil mit Iod: C10H8N2I6 / Synthesis and Crystal Structure of a Polymeric Adduct of 2,2′-Dipyridil and Iodine: C10H8N2I6
Authors: Pohl Siegfried
Published: February 2015

The reaction of 2,2′-dipyridil with iodine (I2; molar ratio 1:3) in CH2Cl2 solution yields the polymeric complex 2,2′-dipyridil(I2)3. The crystal structure of the compound was determined from single crystal X-ray data (monoclinic, C2/c, a = 3215.0(16), b = 439.9(1), c = 1824.1(9) pm, β = 130.79(3)°, Z = 4).

2,2′-Dipyridil(I2)3 forms infinite chains of alternating I6 units and bifunctional dipyridil molecules
Al2Sb2I12: Vierkern-Einheiten in einem 1:1-Addukt aus AlI3 und SbI3 / Al2Sb2I12: Tetrameric Units in a 1:1 Adduct of AlI3 and SbI3
Authors: Pohl Siegfried
Published: February 2015

Al2Sb2I12 (1) was prepared by heating stoichiometric amounts of AlI3 and SbI3 in CS2. The crystal structure of 1 was determined from single crystal X-ray data. The compound crystallizes in the monoclinic space group C2/m with a = 1644.0(3), b = 1318.3(2), c = 728.9(1) pm, β = 119.33(1)°, and Z = 2. The structure was refined by least squares methods to a final unweighted R value of 0.064 for 676 nonequivalent reflections.

The structure is built up of Al2Sb2I12 units in which two Sb-I octahedra share four common edges with two Al-I tetrahedra. As a consequence of the stereochemical activity of the non-bonding electron pair of antimony these cations are displaced from the centers of the iodine octahedra so that three different Sb-I bonds with distances of 270.8, 312.3, and 358.9 pm are observed in 1. The structure of Al2Sb2I12 can also be derived from the layer structures of the BiI3 type
Chemie polyfunktioneller Moleküle, 75 [1]. Das Reaktionsverhalten von 5-Brom-uracil gegenüber Natriumdiphenylphosphid / Chemistry of Polyfunctional Molecules, 75 [1]. The Reaction of 5-Bromo-uracil with Sodium Diphenylphosphide
Authors: Ellermann Jochen , Demuth Alfons A. M.
Published: February 2015

5-Bromo-uracil (1) reacts with sodium diphenylphosphide or a mixture of sodium diphenylphosphide and sodium amide in liquid ammonia to give sodium 5-bromo-uracilate (5 a). From water 5 a crystallizes with one mole H2O yielding 5b. Treatment of 5 a with D2O yields sodium 5-bromo-N-deutero-uracilate-D2O (1/1) (5 c). With chlorodiphenyl-phosphine 5 a forms 1-diphenylphosphino-uracil (2). 5 a, b, c show N(1) · N(3)-(H/D)-tautomerism in concentrated D2O solutions already, but in DMSO or D6-DMSO only in dilute solutions. All the compounds were characterized by infrared, Raman, 1H NMR, UV spectra and conductometry
CIDNP Effects of Sensitized Photochemical Dediazoniation of Arene Diazonium Salts Manipulating CIDNP Intensities by the Experimental Conditions
Authors: Becker Heinz G. O. , Pfeifer Dietmar , Radeglia Reiner
Published: February 2015

13C and 15N photo-CIDNP effects were determined for the reversible electron transfer from pyrene to arene diazonium salts on excitation of the charge transfer band at 360 nm. The diazonium salts being the products of back electron transfer (“cage products”) show enhanced absorption for 13 C(1) and the 15N-enriched diazonium group, whereas the escape products, ArH or 15N2, respectively, yield emission signals. It was shown that the intensities of the CIDNP effects depend on the rates of intersystem crossing kisc within the geminate radical pair, i.e. on the magnetic nucleus used as a probe of the CIDNP effect. Using 1H, 13C or 15N the time domain of observation can be manipulated in the ranges of 90-100 ns, 15-20 ns and 3-5 ns, respectively. Furthermore, the CIDNP intensities depend on the proper balance of the rate of electron back transfer, k-e, and the rate kp of formation of the escape product. Since k-e increases with increasing energy of the geminate radical pair, this balance and therefore the CIDNP intensities vary according to the substituent present and the electron donor used
Molekül- und Gitterbewegungen bei der Umwandlung von trans-L2Mo(CO)4 zu cis-L2Mo(CO)4 im Einkristall / Molecular and Lattice Motions for the Transformation of trans-L2Mo(CO)4 to ciss-L2Mo(CO)4 in a Single Crystal
Authors: Scheidsteger Olaf , Huttner Gottfried , Bejenke Vera , Gartzke Wolfgang
Published: February 2015

Single crystals of trans-L2Mo(CO)4 (L = 1,3-dimethyl-4-imidazolin-2-ylidene) transform to crystals of cis-L2Mo(CO)4 upon heating to 133 °C. X-ray analyses demonstrate that the lattice transformation accompanying the molecular isomerization process is of the martensitic type. Morphological studies reveal that phase boundaries move parallel to close packed planes. The interrelation between lattice movements and intramolecular reorientations is analyzed
Chloroantimonate(III), IV. Darstellung und Kristallstruktur von 2,2′-Bipyridinium-pentachloroantimonat (C10H8N2H2)SbCl5 und der metastabilen Modifikation von 4,4′ -Bipyridinium-pentachloroantimonat (C10H8N2H2)SbCl5 / Chloroantimonates(III), IV. Preparation and Crystal Structures of 2,2′-Bipyridinium Pentachloroantimonate (C10H8N2H2)SbCl5 and of the Metastable Modification of 4,4′-Bipyridinium Pentachloroantimonate (C10H8N2H2)SbCl5
Authors: Lipka Annegret
Published: February 2015

2,2′-Bipyridinium pentachloroantimonate (III) and the metastable modification of 4,4′-bipyridinium pentachloroantimonate(III) were synthezised and investigated by single crystal X-ray diffraction analysis. The structures consist of 2,2′-bipyridinium and 4,4′-bipyridinium cations, respectively, and of pentachloroantimonate anions. With regard to bonding and short intermolecular contacts the coordination of the Sb atoms is distorted octahedral in both structures. Bond lengths of equivalent Sb-Cl bonds differ strongly within the structure of the 2,2′-bipyridinium salt (239.9 pm to 312.1 pm) and are not distinguishable from short intermolecular contacts (305.4 pm and 321.8 pm). In the structure of the 4,4′-bipyridinium salt, bond distances vary only from 240.9 pm to 267.8 pm and are clearly below intermolecular contacts at 318.2 pm. In spite of the different distances the total bond order for each Sb atom is 3. In the structure of the 2,2′-bipyridinium salt the anions build tetramers, whereas in the structure of the 4,4′-bipyridinium salt the anions form chains
γ-Radiolysis of 1,3-Dimethyluracil in N2O-Saturated Aqueous Solutions
Authors: Al-Sheikhly Mohamed , Sonntag Clemens von
Published: February 2015

The γ-radiolysis of N2O-saturated aqueous solutions generates OH radicals and a small amount of H atoms. In 1,3-dimethyluracil solutions (10-3 M) these radicals add mainly to the 5-position of the C(5) -C(6) double bond of the solute. The resulting products have been identified by GC-MS after trimethylsilylation. The major products (G values in brackets) are dimers of the C(5) OH-adduct radicals (3.4), 5,6-dihydro-5,6-dihydroxy-1,3-dimethyl- uracil (0.85), 5,6-dihydro-5-hydroxy-1,3-dimethyluracil (0.75), dimer of the C(5)-OH- adduct with the C(5)-H-adduct radical (0.2) and 5,6-dihydro-6-hydroxy-1,3-dimethyl- uracil (0.2). G( 1,3-dimethyluracil consumption) has been found to be 5.7.

The major reaction in this system is the dimerisation of the primary radicals. To a small extent the primary radicals also disproportionate by electron transfer to give the glycol 5,6-dihydro-5,6-dihydroxy-1,3-dimethyluracil as one of the products. Radiolytically formed H2O2 which could oxidise the C(5)-OH-adduct radical does not contribute to the formation of the glycol because the H2O2 yield is not reduced with respect to its expected “molecular yield” (G = 0.75). In contrast to the uracil system where it has been reported that drastic changes in radiolytic yields occur on going from neutral to alkaline irradiation conditions no such changes have been observed with 1,3-dimethyluracil. However, an acid-catalysed rearrangement from the C(5)-OH-adduct to the C(6)-OH-adduct radical is observed in the present system
Radiation-Induced Degradation of Purine and Pyrimidine 2′-Deoxyribonucleosides in Aqueous KBr Solutions
Authors: Cadet J. , Voituriez L. , Berger M. , Myers L. S.
Published: February 2015

Steady-state γ-radiolysis of 5 × 10-4 M pyrimidine and purine 2′-deoxyribonucleosides in aqueous solutions saturated with N2, N2O and O2, respectively, have been carried out in the presence of 0.1 M KBr. The main final degradation products have been isolated and characterised by various spectroscopic measurements including 1H and 13C NMR, UV, C.D. and mass spectrometry. The radiation-induced decomposition of thymidine is mostly accounted for by an ionic mechanism involving Br2, the decay product of Br2-·, as the reactive oxidising specie. On the other hand the degradation of the purine ring of 2′-deoxy-adenosine and 2′-deoxyguanosine may be accounted for by the action of Br2-·or Br3
·2-
2′,3′ -Dideoxy-3′ -C-(phosphonomethyl)adenosine, the Phosphonate Analogue of 2′-Deoxyadenosine 3′-Phosphate
Authors: Morr Michael , Ernst Ludger , Grotjahn Lutz
Published: February 2015

The title compound 7 is prepared in a five-step synthesis starting from 1,2-di-O-acetyl-5-O-benzoyl-3-deoxy-3-O-(diethoxyphosphonomethyl)-β-D-ribofuranose (2). The preferred conformation of 7 is derived from its 1H and 13C NMR data
A One Step Synthesis of New 4-Aminopyrimidine Derivatives: Preparation of Tetrazolo- and s-Triazolopyrimidines
Authors: Daboun Hamed A. , El-Reedy Ahmed M.
Published: February 2015

2-Mercapto-4-amino-5-cyano-6-arylpyrimidines (1a, b), 2-hydroxy derivatives 1c, d and 2-methylmercapto derivatives 4 a, b were synthesised via the reaction of either a mixture of malononitrile and aromatic aldehyde or arylidene malononitrile with thiourea, urea and S-methylisothiourea, respectively. 1c, d could also be obtained by the action of hydrogen peroxide on 1a, b or by the action of hydrochloric acid on 4a, b. Compounds 4a, b could also be prepared by the action of methyl iodide on 1a, b. 4a reacted with hydrazine hydrate to give the 2-hydrazino derivative 5 which condensed easily with aromatic aldehydes to give the Schiff’s bases 6 a, b. Compound 5 could be converted into the tetrazolo-and s-triazolopyrimidines 7 and 9 by the action of nitrous acid and carbon disulphide respectively. Structures of the newly synthesised compounds were established by chemical routes and spectral studies
Siliciumverbindugen mit starken intramolekularen sterischen Wechselwirkungen, XV [1]. Cycloadditionsprodukte des Tetra-tert-butyldisilens / Silicon Compounds with Strong Intramolecular Steric Interactions, XV [1]. Cycloaddition Products of Tetra-tert-butyldisilene
Authors: Weidenbruch Manfred , Schäfer Annemarie , Thom Karl Ludwig
Published: February 2015

The reaction of 1,1,2,2-tetra-tert-butyl-1,2- dihalodisilanes with alkali metals or metal naphthalenides leads to a complex reaction mixture from which one compound has been identified by its GC/mass spectrum as tetra-tert-butyldisilene (1). The constitution of 1 has been further confirmed by its cycloaddition products with benzil or 1,3-cyclohexadiene, respectively
The Isolation and Structure of Mehranine, a New Indoline Alkaloid from Ervatamia coronaria
Authors: Rahman Atta-ur , Muzaffar Anjum
Published: February 2015

A new indoline alkaloid, mehranine, has been isolated from the leaves of Ervatamia coronaria to which structure 1 has been assigned
Salze der 1.2-Hydrazin-bis(dithiocarbonsäure): Darstellung, Schwingungsspektren und Struktur / Preparation, Vibrational Spectra and Structure of Alkahmetal Salts of the 1,2-Hydrazine-bis(dithiocarboxylic Acid)
Authors: Mattes Rainer , Füsser Bernd
Published: February 2015

The following salts of the 1,2-hydrazine-bis(dithiocarboxylic acid) have been prepared: M2[S2CNH -NHCS2], M = Na, K and M3[S2CN-NHCS2], M = Na, K. In the solvated crystals K2[S2CNH-NHCS2] · 4 CH3OH (a = 718.0(5), b = 1329.3(8), c = 937.7(9) pm, β = 109.26(6)°, space group C2/m, Z = 2) the [S2CNH-NHCS2]2- ion possesses crystallographic C2h symmetry, i.e. a trans planar structure with a N-N bond length of 139.2(3) pm. Vibrational spectra indicate a lower symmetrical anion in the unsolvated crystals. In the trianion [S2CN-NHCS2]3- the C-N stretching vibrations are observed at 1400 and 1310 cm-1.
Phosphinsubstituierte Chelatliganden, IX [1]. NMR-Spektren und Kristallstruktur von Diphenyl(thio)phosphoryl-N,N-dimethylthioformamid / Phosphine Substituted Chelate Ligands, IX [1]. NMR Spectra and Crystal Structure of Diphenyl(thio)phosphoryl-N,N-dimethylthioformamide
Authors: Bruns Andreas , Hiller Wolfgang , Kunze Udo
Published: February 2015

The P=S and P=0 derivatives 2a, b of diphenylphosphino N,N-dimethylthioformamide (1) were obtained by addition of sulfur to 1 and by Arbusov reaction of Ph2POMe with Me2NC(S)Cl, respectively. The position of the cis-P N-methyl proton signal is markedly affected by the P = X group which exerts a diamagnetic shift for X = S (2a) but a paramagnetic shift for X = O (2b) relative to 1. Unusually small 3JPC couplings are observed in the 13C{1H} NMR spectrum. The P-sulfide 2 a crystallizes in the monoclinic space group C2/c with the lattice constants a = 1791.5(3) pm, b = 686.7(2) pm, c = 2591.3(4) pm, β = 93.10(4)°. The molecule structure is characterized by a planar thioamide unit with the P=S group forming an angle of 53.4° to the plane.
Ba5(GaS4)2: Das erste ortho-Thiogallat(III) / Ba5(GaS4)2: The First ortho-Thiogallate(III)
Authors: Eisenmann Brigitte , Jakowski Mareike , Schäfer Herbert
Published: February 2015

The new compound Ba5(GaS4)2 crystallizes in the orthorhombic system (space group: Cmca) with lattice constants a = 2249.4(12) pm, b = 1214.6(8) pm, c = 1188.7(8) pm. In the structure there are isolated GaS4
5- -tetrahedra. According to stoichiometry and structure this compound belongs to the complex salts, and is the first othiogallate(III).
Ein neuer Wasserstoffbrücken-Typ: Intramolekulare S—H···S-Brücken in Dithiotropolon / A Novel Type of Hydrogen Bond: Intramolecular S—H···S-B ridges in Dithiotropolone
Authors: Krebs Bernt , Henkel Gerald , Stücker Wolfgang
Published: February 2015

In dithiotropolone (2-mercaptocycloheptatrienethione) a novel type of S - H···S hydrogen bond is observed from spectroscopic results and from a single crystal X-ray structure analysis. Intramolecular S-H···S bonds with a very short S ··· S separation of 3.13 Å and with d(S···H) = 2.10 Å, ∢ (S-H···S) = 136° are formed, the S-H stretching frequency of 2450 cm-1 being lowered by about 120 cm-1 from the value for the free SH group. A different relationship between S···S bridge bond distances and S-H stretching frequencies applies as compared to the intermolecular bridges of thiophosphinic and thiocarbonic acids. Crystalline dithiotropolone is monoclinic, space group P21/c, Z = 8, with a = 8.352(2), b = 13.806(4), c = 12.371(2) Å, β= 103.46(2)°.
Zur Reaktion von Metall-koordiniertem Kohlenmonoxid mit Yliden, XVIII [1]. Eisenacyl-phosphorylide mit Isonitril-substituiertem Metallzentrum [2] / Reactions of Metal-Coordinated Carbon Monoxide with Ylides, XVIII [1]. Ironacyl Phosphorus Ylides with an Isocyanide-Substituted Metal Centre [2]
Authors: Stasunik Andrea , Malisch Wolfgang
Published: February 2015

The thermal or photochemical reaction of [Cp(CO)3Fe]BF4 with the isocyanides MeNC and tBuNC provides ready access to the salts [Cp(CO)(CNR)2Fe]BF4 [R = Me (2a); tBu (2b)] and [Cp(CNR)3Fe]BF4 [R = Me (3a); tBu (3b)]. Treatment of 2a, b and [Cp(CO)2(MeNC)Fe]BF4 with two moles of Me3P=CFT leads to the formation of the ironacyl ylides Cp(RNC)2Fe- C(O) -CH=PMe3 [R = tBu (4a); Me (4b)] and Cp(CO)(MeNC)FeC(O)CH = PMe3 (4c), respec­tively, via ylide attack at the carbonyl carbon and subsequent transylidation. While 4a is isolable, 4b, c were detected only in solution. 4a is easily cleaved by Mel and MeOSO2F to give [Cp(CO)(tBuNC)2Fe]X and [Et2Me2P]X [X = I (5a); SO3F (5b)], which suggests preferred addi­tion of the carbon electrophile at the “ylidic” carbon, followed by dissociation of the carbon(acyl)- carbon(ylide) bond.
Formation of Radical Trications and Diradical Dications by the Polarographie Reduction of 1,1"-Alkanediyl-bis- (1'-alkyl-4,4'-bipyridinium) Tetraquaternary Salts
Authors: Attalla Moetaz I. , McAlpine Neale S. , Summers Lindsay A.
Published: February 2015

Six 1′,1″-alkanediyl-bis(1′-alkyl-4,4'-bipyridinium) tetraquaternary salts have been prepared and their reduction and redox properties studied by polarography and cyclic voltammetry. They are reduced to radical trications and diradical dications at potentials (Ec) of about -0.20 V and -0.35 V, respectively.
Gehinderte Ligandenbewegungen in Übergangsmetallkomplexen, XXII [1]. Synthese und Moleküldynamik von OctacarbonyI-μ-(η2:1-ethinyl)-μ-hydrido-dirheniuni(I) / Hindered Ligand Movements in Transition Metal Complexes, XXII [1]. Synthesis and Molecule Dynamics of Octacarbonyl-μ-(η2:1-ethynyl)-μ-hydrido-dirhenium(I)
Authors: Franzreb Karl Heinz , Kreiter Cornelius G.
Published: February 2015

UV-irradiation of decacarbonyl-dirhenium(0) (1) and acetylene in hexane yields a mixture of complexes, which were separated by preparative HPL-chromatography and characterized by elemental analysis, IR, NMR and mass spectroscopy. Main product of the reaction is octa- carbonyl-μ-(η2:1-ethynyl)-μ-hydrido-dirhenium(I) (4). Tricarbonyl-η5-methylcyclopentadienyl- rhenium(I) (2) and tetracarbonyl-2-3:9-η-(8,10-dinorborna-2,5-dien-9-yl)-rhenium(I) (3) are ob­tained in moderate yields. Minor by-products of the reaction are octacarbonyl-μ-hydrido-μ-η2:1- vinyl-dirhenium(I) (5), tridecacarbonyl-μ-η2:1-vinyl-trirhenium (6) and HRe3(CO)14 (7). 4 shows a hindered ligand movement of the η2:1-ethynyl bridge, with ⊿G≠
250
= 48.2 kJ · mol-1.
NOTIZEN. Darstellung und Kristalldaten der isotypen Wismut-Oxid -Halogenide Bi5O7I und Bi5O7Br / Preparation and Crystal Data of the Isotypic Bismuth Oxide Halides Bi5O7I and Bi5O7Br
Authors: Ketterer J. , Krämer V.
Published: February 2015

The title compounds were prepared (a) polycrys­talline by sintering the binary components and (b) single-crystalline by a wet chemical method. They crystallize in the space group Cmca with the lattice parameters a = 16.244(2), b - 5.342(1), c = 23.006(4) and 16.099(2), 5.296(1), 22.995(6) Å, resp. Their X-ray powder diffraction data are listed.
Synthese von (Me3Sn)4Sb2 durch Luft-Oxidation von (Me3Sn)3Sb /Synthesis of (Me3Sn)4Sb2 by Air-Oxidation of (Me3Sn)3Sb
Authors: Breunig Hans Joachim
Published: February 2015

Oxidation of (Me3Sn)3Sb in air gives (Me3Sn)2O and (Me3Sn)4Sb2 in 45% yield.
Graphite Intercalation Compounds with Tin Tetrachloride
Authors: Schlögl Robert , Boehm Hanns-Peter
Published: February 2015

Intercalation compounds of graphite with SnCl4 have been prepared by reaction in SOCl2/CCl4 or by UV irradiation in CCl4 or 1,2-dichloroethane. Mix­tures of 1st, 2nd, and 3rd stages have been obtained. Chemical analyses and 119Sn MöBbauer spectra indi­cate that SnCl6
2- ions are intercalated. Solvent molecules are co-intercalated.
Die Kristallstruktur von SrSb4S7 • 6 H2O / The Crystal Structure of SrSb4S7 • 6 H2O
Authors: Cordier Gerhard , Schäfer Herbert , Schwidetzky Christoph
Published: February 2015

The new compound SrSb4S7 · 6 H2O crystallizes in the monoclinic system, space group P21/n with lattice constants a = 2765,4(8) pm, b = 731,5(3) pm, c - 897,2(3) pm, ß - 90,4(1)°. In the structure there are anionic (Sb4S7
2-)∞-strings, which are arranged parallel in sheets and separated by the hydrated Sr2+ ions
ReCl5 • OPCl3; IR-Spektrum und Kristallstruktur / ReCl5 • OPCl3; IR Spectrum and Crystal Structure
Authors: Klingelhöfer Paul , Müller Ulrich , Hauck Hans Günter , Dehnicke Kurt
Published: February 2015

Single crystals of ReCl5 • OPCl3 were obtained by cooling a saturated solution of rheniumpentachloride in phosphorylchloride. It formes black needles, which are extremely sensitive to moisture. In the IR spectrum ν(PO) is shifted downwards by 140 cm-1 in comparison with liquid POCl3, indicating coordination via oxygen. The crystal structure was solved and refined from Xray diffraction data (space group Pnma, four formula units per unit cell, a = 1629, b = 790, c = 877 pm, 902 observed, independent reflexions, R = 0.040). The complex forms discrete molecules ReCl5 • OPCl3, with symmetry Cs(m). Bond lengths are Re -O - 214 pm and P-O = 146 pm, the angle Re -O -P is 143°
Darstellung und Struktur von 1.2.5.6-Tetraphospha-3.4-7.8-dibenzo-2.6-diiodo-bicyclo[3.3.0]octan / Synthesis and Structure of l,2,5,6-Tetraphospha-3,4-7,8-dibenzo-2,6-diiodo-bicyclo[3,3,0]octane
Authors: Wörz H.-J. , Pritzkow H. , Latscha H. P.
Published: February 2015

The reaction of o-phenylenebis(dichlorphosphane) (3) with Lil in benzene gives 1,2,5,6- tetraphospha-3,4-7,8-dibenzo-2,6-diiodo-bicyclo[3,3,0]octane (4a), whose structure is reported. The bicyclus is also characterized by elemental analysis, 1H NMR, 31P NMR, IR, mass spectroscopy
Spaltung von S4N4 zu S2N2 bei Raumtemperatur: Darstellung und Struktur von S2N2 • 2AlBr3 / Cleavage of S4N4 to S2N2 at Room Tem perature: Preparation and Structure of S2N2 • 2AlBr3
Authors: Thewalt Ulf , Holl Konrad
Published: February 2015

The compound S2N2 • 2AlBr3 has been prepared by reaction of S4N4 with AlBr3 in 1,2-dibromoethane at room temperature. Its crystal and molecular structure have been determined by X-ray diffraction; R = 0.068. Crystal data: monoclinic, P 21/n, a = 9.594(5), b = 9.975(4), c = 7.528(4) Å , β = 111.36(5)°. The S2N2 ring of the centrosymmetrical complex is bonded via its nitrogen atoms to two AlBr3 units thus completing coordination tetrahedra around the Al atoms. Bond distances and angles within the S2N2 ring are d(S-N) = 1.629(13) and 1.651(13) Å, ∢ (S-N-S) = 95.8, and ∢ (N-S-N) - 84.2°. Whereas the S-N bond lengths agree closely with those of free S2N2, the angle at N is enlarged by ca. 5° and the angle at S is decreased by ca. 5°. The sulfur atoms form two close S···Br contacts of length 3.149 (intramolecular) and 3.193 (intermolecular) Å , respectively. The intermolecular attractive nonbonded S···Br interactions tie the complexes together in a way that leads to infinite chains which run parallel to the crystallographic z axis
Reaktionen von Metallkomplexen mit kleinen Ringen, XI [1] Ringöffnung von Aziridinen mit Metallcarbonylhydriden; β-Aminoacylchelat-Komplexe von Mangan, Molybdän, Wolfram und Cobalt / Reactions of Metal Complexes with Small Rings, XI [1] Ring Opening of Aziridines by Metal Carbonyl Hydrides; β-Aminoacyl Chelate Complexes of Manganese, Molybdenum, Tungsten and Cobalt
Authors: Danzer Wolfgang , Höfer Roland , Menzel Hartmut , Olgemöller Bernhard , Beck Wolfgang
Published: February 2015

The metal carbonyl hydrides HM(CO)3(π-C5H5) (M = Mo, W), HMn(CO)4L, HCo(CO)3L (L - CO, PPh3) react with aziridines by protonation of aziridine, nucleophilic attack of the corresponding carbonyl metallate and CO insertion to give the β-aminoacyl complexes 2-7. The ring opening of C-substituted aziridines is regiospecific. With alkyl substituted aziridines the nucleophilic attack of the carbonyl metallate occurs at the sterically less hindered carbon atom, with phenyl substituted aziridines at the phenyl substituted carbon atoms. From the reactions of HM(CO)3(π-C5H5) with optically active aziridines, which afford complexes with an asymmetric metal atom, only one diastereomer could be observed. The mechanism of these reactions is discussed and the spectral data (IR, 1H NMR, MS) of the complexes are reported. β-Aminoacyl complexes have also been obtained by addition of amines to [(π-C5H5)(CO)3M(alkene)]+BF4
- (M = Mo, W).

The methyl complex H3CMn(CO)5 reacts with aziridine to give the acetyl complexes H3CC(O)Mn(CO)4(aziridine) and H3CC(O)Mn(CO)3(aziridine)2, respectively
Darstellung, 11B-NMR- und Schwingungsspektren isomerenreiner Halogenohydrododecaborate XnB12H12–n
2–; X = Cl, n = 1–3; X = Br, n = 1,2; X = I, n = 1 / Preparation, nB NMR and Vibrational Spectra of Pure Isomeric Halohydrododecaborates XnB12H12-n
2-; X = Cl, n = 1-3; X = Br, n = 1,2; X = I, n = 1
Authors: Srebny H.-G. , Preetz W. , Marsmann H. C.
Published: February 2015

Pure isomers of XnB12H12-n
2-; X = Cl, Br, I are isolated by ion exchange chromatography on diethylaminoethyl cellulose. The structures are determined by 11B and 11B {1H}NMR spectroscopy. With X = Cl, Br the signal of ipso-B atomes is shifted to lower, with X = I to higher field compared with B12H12
2-. The resonances of B-atoms influenced by the antipodal effect are observed at high field, increasing within the series I<Br<Cl. The chemical shifts are explained by the anisotropy effect and by the paramagnetic term due to different -I and +M effects of the halogens. In agreement with theoretical predictions the substitution of B12H12
2- with chlorine proceeds successively at vicinal positions B(1) -B(2) -B(3). The IR and Raman spectra of 1-XB12H11
2- show in the region 175 - 380 cm -1 two characteristic bands shifting to lower frequencies in the series Cl, Br, I and are therefore assigned to (B12) -X stretching and (B12) -X bending modes, respectively
6π-Tricarbonyl-Komplexe von Pyridin-Derivaten, Synthesen und Reaktionen / 6π-Tricarbonyl-Chromium Complexes of Pyridine Derivatives, Syntheses and Reactions
Authors: Dimroth Karl , Thamm Rüdiger , Kaletsch Hans
Published: February 2015

New 6π-tricarbonylchromiumpyrnftne complexes 5c and 5d could be synthesized from 2,6-di-rbutyl- and 2,4,6-tri-f-butylpyridines (3c and 3d) with chromium hexacarbonyl. They are characterized by their 1H and 13C NMR Spectra and their CO-frequencies which are rather similar to those of 6π-tricarbonylchromium-2,4 ,6-triphenyl [1] or 2,4,6-trw-butyl- [2] λ3-phosphorins. When 5d is reacted with lithiumphenyl, the phenyl residue adds to C-4, giving probably compound 7, which by methanolysis and allyl rearrangement of the hydrogen atom from position 4 to position 2 affords tricarbonylchromium-2,6-di-f-butyl-4-phenyl-1,2-dihydropyridine (8) in 56% yield. The 6π-tricarbonylchromium complexes of 2,4,6-triphenyl- or 2,4,6-tn-t-butyl-λ3-phosphorins react with lithiumorganic compounds by addition only to the phosphorus atom whose reaction with methyliodide lead to tricarbonylchromium-λ5-phosphorin-ylid complexes [2], 5 d is a well crystallized compound, the X-ray analysis of the first 6π-tricarbonylchromium pyridine derivate could be performed [3] and compared with the results of the X-ray analysis of 6π-tricarbonylchromiumx 2,4,6-triphenyl-λ3-phosphorin [4]
Die Kristallstruktur von Tricarbonyl(2.6-di-tert-butyl-pyridin)chrom(0) bei 200 K / Crystal Structure of Tricarbonyl(2,6-di/tert-butyl-pyridine)chromium(0) at 200 K
Authors: Schmidt Roland E. , Massa Werner
Published: February 2015

Based on single crystal X-ray diffraction data the crystal structure of tricarbonyl(2,6-dwmbutyl- pyridine)chromium(0) has been determined at 200 K: space group P 21/n, Z = 4, lattice constants a = 680.6(5), b - 1383.3(10), c = 1763.0(16) pm, β = 96.53(8)°, refinement to Rw - 0.048 for 1672 independent reflections with FO > 2 σ. The chromium atom is η6π6- bonded to the essentially planar pyridine ring (Cr-C: 219-222 pm, Cr-N: 221 pm). The CO ligands show “eclipsed” orientation with respect to the 2, 4 and 6 position of the pyridine ring. Two CO groups fit into the gaps formed by two methyl groups of the tert-butyl substituents in 2 and 6 position, respectively. The results are discussed in context with related arene and λ3-phosphorine complexes
Fast Atom Bombardment Mass Spectrometry of the Vitamin B12 Analogues Hydrogenobalamin and Cupribalamin
Authors: Grotjahn Lutz , Koppenhagen Volker B. , Ernst Ludger
Published: February 2015

Hydrogenobalam in (metal-free vitamin B12) and cupribalamin are characterized by their fast atom bombardment (FAB) mass spectra which show molecular ion and characteristic fragment ion peaks. These spectra and the high-resolution FAB mass spectrum of cobalamin (vitamin B12) show that the (M+H)+-CN-59 peak for the latter is due to loss of acetamide and not of the central cobalt atom. In the FAB mass spectrum of cupribalamin metal clusters are observed
Tetraphenylarsonium-tetraoxoosinat (VII), AsPh4[OsO4] / Tetraphenylarsonium Tetraoxoosm ate (VII), AsPh4[OsO4]
Authors: Bilger Edgar , Pebler Jürgen , Weber Rainer , Dehnicke Kurt
Published: February 2015

AsPh4[OsO4] is prepared by reaction of OsO4 with AsPh4I in CH2C12 solution. According to the IR spectrum , the [OsO4]⊖ ion adopts a distorted tetrahedral structure. The reciprocal magnetic susceptibility displays linear temperature dependence in the range of 4.2 to 140 K (μeff( = 1.25 B.M., 0 - 2.6°). The results of cyclo-voltammetric measurements are in accordance with a reversible oneelectron process OsO4/OsO4
⊖; the redoxpotential was found to be 104(2) and 100(3) mV resp. versus SCE
Phthalocyaninatoeisen-Cyanid- Verbindungen: Synthese und elektrische Leitfähigkeiten / Cyanide Containing Phthalocyaninatoiron Compounds: Synthesis and Electrical Conductivities
Authors: Hanack Michael , Schneider Otto
Published: February 2015

The preparation of cyanide containing phthalocyaninatoiron(II) or -iron(III) derivatives either with terminal or bridging cyanide is described. With help of the C≡N valence frequency (IR) and the magnetism of the compounds the oxidation state of the iron is determined. Thermoanalytical and electrical conductivity data are reported
Fluoride und Fluorosäuren, VII [1]. Kristallstrukturen von Säurehydraten und Oxoniumsalzen, XXII [2]. Hydratbildung der Trifluoressigsäure sowie Strukturen eines Monohydrats und eines Tetrahydrats [3]. / Fluorides and Fluoro Acids, VII [1] Crystal Structures of Acid Hydrates and Oxonium Salts, XXII [2]. Hydrate Formation of Trifluoroacetic Acid and Structures of a Monohydrate and a Tetrahydrate [3]
Authors: Mootz Dietrich , Boenigk Dagmar
Published: February 2015

The liquidus and solidus lines of the quasi binary system CF3COOH-H2O were determined by low temperature difference thermal analysis and the resulting phase relations controlled by X-ray powder diffraction. Formation of a monohydrate and a tetrahydrate, melting congruently at -43 and -16 °C, respectively, is confirmed. In addition a metastable form of the monohydrate and a low temperature form of the tetrahydrate, stable below -47 °C, are indicated. The crystal structures of the stable high temperature forms were determined. From these the monohydrate (tetragonal, space group I42d, Z = 16) is a true acid hydrate, CF3COOH-H2O, and the tetrahydrate (triclinic, P1̅, Z = 2) a hydrated oxonium salt, (H5O2)+[H(CF3COO)2]- · 6H2O.
Element—Element-Bindungen, III [1]. Intermolekulare Sb···Sb-Wechselwirkungen im kristallinen Tetramethyldistiban1 / Element—Element Bonds, III [1]. Intermolecular Sb···Sb Interactions in Crystalline Tetramethyldistibane
Authors: Mundt Otto , Riffel Heinz , Becker Gerd , Simon Arndt
Published: February 2015

Tetramethyldistibane which shows a colour change from deep red to pale yellow upon melting,

has been subjected to single-crystal x-ray diffraction analyses at -21° and -139 °C (orthorhombic,
Pnma, Z = 4, -139 °C: a = 1150.9(3); b = 1136.8(2) ; c = 651.6(2) pm). The molecules adopt
the antiperiplanar conformation with the crystallographically imposed symmetry m (Cs) and are
aligned in extended linear antimony chains with short intermolecular contacts (-139 °C: Sb-Sb
283.8(1), Sb···Sb 367.8(1) pm; Sb-Sb---Sb 179.2°). The structure is compared with those of
similar compounds.
Carbonylniobchemie, VII. Die 31P—NMR-Spektren der Phosphinderivate des [Nb(η5-C5H5)(CO)4] / Carbonyl Niobium Chemistry, VII. The 31P NMR Spectra of Phosphine Derivatives of [Nb(η5-C5H5)(CO)4]
Authors: Rehder Dieter , Bechthold H.-Ch.
Published: February 2015

δ(31P) NMR data of the complexes [Nb(Cp)(CO)3PZ3] (Cp = η5-C5H5) and cis- [Nb(Cp)(CO)2(PZ3)2] [Z = H, R (alkyl and aryl), OR, NMe2, PR2] are interpreted on the basis of varying P(3pσ) and P(3dπ) contributions to the bond-order density matrix in the paramagnetic deshielding term of the overall shielding constant. For Z = R, shielding of the 31P nucleus of the coordinated phosphine decreases as the cone angle θ increases, as a result of increasing p contribution. For Z = OR and NMe2, P-Nb π interactions dominate, and the decrease of the P(3dπ) occupation with increasing θ leads to an increase of shielding. In the case of alkoxiphosphines, decreasing 31P shielding is accompanied by an increase of the shielding of the metal nucleus [quantified here by δ(51V) of the vanadium complexes], while, for the substantially less powerful π interacting alkylphosphines, shielding trends for the two nuclei parallel each other. Coordination shifts Δδ(P) are somewhat greater for small phosphines but, spanning a range of 80 ± 30 ppm, tend to be comparatively invariant. In [V(Cp)(CO)3PZ3], the 31P nucleus is deshielded by 10 to 30 ppm with respect to the corresponding niobium complexes.
Crystal Structure and Mössbauer Spectroscopic Investigation of the Low Temperature Molecular Dynamics of Hexa(2-ethylimidazole)iron(II) Hydridotetracarbonylferrate(-II)
Authors: Bill E. , Blaes N. , Fischer K. F. , Gonser U. , Pauly K. H. , Preston R. , Seel F. , Staab R. , Trautwein A. X.
Published: February 2015

The title compound 1 was synthesized as reaction product of pentacarbonyl iron with 2-ethylimidazole. A Zerewitinoff-determination shows that we are rather dealing with hydrido-tetracarbonylferrate(- II) than with tetracarbonylferrate(-I) as supposed in a preceding paper. A new crystal structure analysis of 1 was performed. With respect to [HFe(CO)4]- we found that three CO groups are ordered with normal tetrahedral angles, while the fourth CO group shows statistical distribution over three sites (disordered sites). The temperature parameters of the disordered CO sites are considerably more anisotropic than those of the ordered CO sites. Experimental Mössbauer spectra have been recorded between 4.2 K and 288.7 K. 1 exhibits a Mössbauer pattern with two subspectra, one for each of the cations and the anions. The cation subspectrum reflects normal ferrous high-spin behavior, while the anion subspectrum shows peculiar anomalies around 200 K. On the basis of our X-ray structure results molecular orbital calculations have been performed with the aim of deriving electric field gradient tensors for the various stochastic substates of [HFe(CO)4]-. These tensors were then used within the frame on an analytical lineshape formula. It turns out that the statistical distribution of the fourth CO group over three sites is associated with a jump behavior, similar to trapped diffusion, of the CO group among the three sites and not with static disorder. The Fe atom follows this jumb behavior, however, its triangular displacement body with jump distance d ~ 0.30 Å is considerably smaller than that of the CO group.
Atran-analoge Verbindungen des Typs / Atrane Analogous Compounds of the Type
Authors: Grobe Joseph , Henkel Gerald , Krebs Bernt , Voulgarakis Nikolaos
Published: February 2015

Heterocyclic cage compounds of type I (compounds 8-10) have been prepared by condensation reactions of 1,2,2-trifunctional disilanes Me(R)XSiSiMeX2 (R = Me, Ph, OEt; X = NMe2, OEt) with triethanolamine using the “Dilution Principle”. The starting compounds are obtained by Si-Me cleavage of Si2Me6 with acetylchloride/AlCl3 followed by either aminolysis with HNMe2 or alcoholysis with EtOH. 1H NMR spectra indicate N→Si(1) intraction with the more acidic Si atom in 8 and 9. This result is proved by the X-ray structure analysis of 8 (monoclinic, P21/c; a = 7,088(2), b = 15,070(4), c = 12,701(4) Å, β = 104,96(2) at -130 °C, Z = 4); the Si(1)···N distance is found to be 2,768 Å , connected with a significant angular distortion of the tetrahedral coordination around Si(1) towards a trigonal bipyramid. In compound 10, too, N→Si(1) coordination is observed at room temperature in spite of almost equal acidity for both Si atoms. This can be explained by the preference of 5- over 6-membered chelating ring systems. At higher temperatures the 1H NMR spectra show a fluctuation of the N-donor between the two Si centres.
Über einige Redox-Reaktionen von Iodgallanen und lodindanen mit organischen Disulfiden / Some Redox Reactions of Iodogallanes and Iodoindanes with Organic Disulfides
Authors: Hoffmann Gerhard G.
Published: February 2015

The redox reactions between the iodogallanes Gal3 as well as PhGaI2 and the disulfides CH3SSCH3 and PhSSPh lead to the monoalkylthio- and monoarylthiogallanes CH3SGaI2 and PhSGaI2 respectively. No reaction occurs between Inl3 and these disulfides, whereas, surprisingly, Phlnl2 does react to give the monoalkylthio- and monoarylthioindanes CH3SInI2 and PhSInI2, respectively, Ph2GaI and Ph2InI form only the thioether adducts with the disulfides, which were not isolated. Initative mechanisms of these reactions are reported.
Versuche zur Synthese 2.2′-disubstituierter cis-Bis(phenyl)bis(triphenylphosphan)platin(II)-Verbindungen und Kristallstruktur des cis-Bis(2-nitrophenyl)bis(triphenylphosphan)platin(II) / On the Formation of 2,2′-Disubstituted cis-Bis-(phenyl)bis(triphenylphosphane)platinum(II) Compounds and Crystal Structure Determination of cis-Bis(2-nitrophenyl)bis(triphenylphosphane)platinum(II)
Authors: Brune Hans-Albert , Wiege Manfred , Debaerdemaeker Tony
Published: February 2015

Syntheses of 2,2′-disubstituted cis-Bis(phenyl)bis(ligand)platinum(II) compounds are described with respect to the influence of the ortho-substituents on reaction paths. Configuratior and conformation of the substituted phenyl rings are established by an X-ray structure determination of cis-Bis(2-nitrophenyl)bis(triphenylphosphane)platinum(II).
Die Kristallstrukturen von cis- und trans-Dichlorstilben
Authors: Hey Evamarie , Weller Frank , Dehnicke Kurt , Maier Günther
Published: February 2015

The crystal structures of cis- and trans-dichlorostilbene were determined from X-ray diffraction data, cw-dichlorostilbene crystallizes in the rhombohedral space group R3̄ with 18 formula units per unit cell (821 observed independent reflexions, R = 0.064) with the dimensions a = b = 3323, c = 601 pm, γ = 120°. The molecule corresponds to the point group C1 with a C = C bond length of 133 pm; the dihedral angles of the phenyl rings with the corresponding C = C-Cl plane are 48° and 72°, respectively. Trans-dichlorostilbene crystallizes in the monoclinic space group P21/n with two formula units per unit cell (1138 independent reflexions, R = 0.056) with the dimensions a = 572, b = 1733, c = 641 pm, β = 111°. The molecule is centrosymmetric (Ci) with a C = C bond length of 133 pm; the dihedral angle of the phenyl rings and the Cl - C = C plane is 71°. The stilbene molecules are disordered about the centre of symmetry in two orientations with the ratio 3:7.
Darstellung kationischer mer-Phosphit-substituierter Mangancarbonyl-Verbindungen/Synthesis of Cationic Mer-Phosphite-Substituted Carbonylmanganese Compounds
Authors: Berke Heinz , Weiler Gertrud
Published: February 2015

Di-, tri- and tetrasubstituted carbonylmanganese compounds (OC)nL6-nMn+PF6
- (L = P(OMe)3, P(OEt)3, P(O-i-Pr)3, P(OPh)3 and P(O-o-Tolyl)3) are synthesized by hydride abstraction and substitution processes from corresponding hydridemanganese compounds.
2-Amino-3.5.6-trichloro-1.4-benzochinon durch Ammonolyse von Chloranil/2-Am ino-3,5,6-trichloro-1,4-benzoquinone: the Primary Ammonolysis Product of Chloranil
Authors: Endres Helmut , Rossato Elisabeth , Balles Rainer
Published: February 2015

C6H2Cl3NO2, the hitherto unknown intermediate in the preparation of 2,5-diamino-3,6-dichloro-1,4-benzoquinone by ammonolysis of chloranil, the mono-substituted title compound, was obtained in 18% yield. It crystallizes in the orthorhombic space group D4
2-P212121, a = 4.941(3), b = 10.725(4), c = 15.400(5) Å , V = 816.1 Å3, Z = 4, Mr = 226.44, dc = 1.84 gcm-3. Final Rw = 0.035 for 780 observed independent reflections.
Die Kristallstrukturen des Benzo[1.2-c:3.4-cʹ]bis[1.2.5]thiadiazols und des semihomologen [1.2.5]Selenadiazolo[3.4-e]-2.1.3-benzothiadiazols [1]/The Crystal Structures of the Benzo [1,2-c : 3,4-cʹ]bis[1,2,5]thiadiazole and of the Semihomologous [1,2,5]Selenadiazolo[3,4-e]-2,1,3-benzothiadiazole [1]
Authors: Gieren Alfred , Betz Helmut , Hübner Thomas , Lamm Viktor , Neidlein Richard , Droste Dao
Published: February 2015

The X-ray structure analyses of the title compounds 1 and 2 were performed. 1: monoclinic, C 2/c, a = 9.532(2), b = 11.469(2), c = 7.030(3) Å, β = 110.58(2)°, Z = 4; 2: monoclinic, P21/a, a = 7.650(2), b = 7.729(2), c = 12.948(3) Å, β = 74.26(2)°, Z = 4. The structure of 1 was solved by direct methods, that of 2 by Patterson- and successive Fourier-synthesis techniques. The least squares refinement converged for 894 independent reflections with I > 2δI to an R-value of 0.032 (Rw = 0.035) in the case of 1 and for 1440 independent reflections to an R-value of 0.045 (Rw = 0.045) in the case of 2. The bond lengths in the [1,2,5]thiadiazole rings in 1 and 2 and also in the Se-homologous ring in 2 indicate to a quasi-aromatic π-system, whereas the aromatic character of the central benzene ring in 1 and 2 is strongly disturbed. The substitution of one S by the homologous Se in 2 induces significant changes of comparable bond lengths in 1 and 2. In the crystal structures of both compounds molecular layers and columnar stacks are formed. Quasipolymers in form of ribbon like structures are established in 1 by short S···N contacts and in 2 by short Se···N contacts. In 2 (SeN2)x-chains are formed.
The Isolation and Structure of “Moenjodaramine” and “Harappamine” — Two New Alkaloids from Buxus papilosa
Authors: Rahman Atta-ur , Nisa Mehrun , Farhi S.
Published: February 2015

Two new alkaloids, have been isolated from the leaves of Buxus papilosa which are the first members of a new group of pentacyclic natural products bearing both a tetrahydro-oxazine ring and a 9(10→19) abeo-diene system. The alkaloids, named "moenjodaramine" and “harappamine”, have been assigned structures ( 1) and ( 2) respectively on the basis of spectroscopic studies.
Analogs of the Luteinizing Hormone Releasing Hormone having the Azagly10 Moiety with Antiovulatory Activity
Authors: Folkers Karl , Bowers Cyril Y. , Stepinski Janusz , Plucinski Tomasz , Sakagami Masanori , Kubiak Teresa
Published: February 2015

Twenty-four new analogs of the luteinizing hormone releasing hormone (LHRH) were synthesized and bioassayed for antiovulatory activity in rats. [N-Ac-3⊿Pro1, pF-D-Phe2, D-Trp3,6, Azagly10]-LHRH com pletely inhibited ovulation at 6 μg and was the most potent of the 24, and is a relatively potent antagonist in the field. The Azagly- and Ac-NHNH- and D-Alamoieties in position 10, and D-Arg in position 6, and diverse substitutions in position 1 were emphasized. D-Arg6 was inferior to D-Trp6, and pCl-D-Phe6 appeared superior to D-Trp6. D-Trp3,6 was superior to D-2-Nal3,6 and D-His3,6.
Notizen: 15N NMR Study of Tris(dimethylamino)phosphine Derivatives: (Me2N )3PSe, (Me2N)3PTe and (Me2N)3PBH3
Authors: Wrackmeyer Bernd
Published: February 2015

The title compounds have been studied by 11B, 15N, 31P, 77Se and 125Te NMR spectroscopy (δ-values, coupling, constants). The 15N relaxation is dominated by 15N-1H dipolar interactions whereas nuclear screening anisotropy controls the 125Te relaxation.
Notizen: Darstellung und Eigenschaften von und Reaktionen mit metallhaltigen Heterocyclen, XXXVIII [1] Fünf- und sechsgliedrige Oxaphosphamolybdacycloalkane durch reduktive Cycloeliminierung/Preparation and Properties of, and Reactions with, Metal-Containing Heterocycles, XXXVIII [1] Five- and Six-Membered Oxaphosphamolybdacycloalkanes by Reductive Cycloelimination
Authors: Lindner Ekkehard , Brösamle Andreas
Published: February 2015

The reductive cycloelimination of the complexes Lm(Br)MoPPh2O(CH2)n-Cl (3a,b) [n = 2 (a), 3 (b); LmMo = η5-C5H5Mo(CO)2], which can be obtained from the reaction of PPh2O-(CH2)n-Cl (1a, b) and Lm(Br)MoCO (2) in n-hexane/THF, results in the formation o f the metallacycles

(4a,b). Compared with

the five-membered heterocycle 4a is thermally more stable.
Chemische Redoxreaktionen von Dreikernclustern / Chemical Redox Reactions of Trinuclear Clusters
Authors: Honrath Ute , Vahrenkamp Heinrich
Published: February 2015

The clusters ECo3(CO)9 (E = S, PPh) can be converted with one electron oxidants to their cations which are only stable in solution. Reduction of EFeCo2(CO)9 (E = S, PPh) with sodium naphthalenide or cobaltocene produces the anions which are stable as PPN+ or CoCp2
+ salts. The clusters RPCo3(CO)9 (R = Ph, NEt2, OBu) react with iodine to form the tetranuclear clusters (RP)2Co4(CO)10
Eine Notiz über Li4[PbO4] [1, 2] / A Note on Li4[PbO4] [1,2]
Authors: Stoll Helmut , Hoppe Rudolf
Published: February 2015

The crystal structure of Li4PbO4 is reexamined by new X-ray data [Ag-Kα, four-circle-diffractometer CAD 4 (Enraf-Nonius), 863 of 890 Io, R = 1,88% and Rw = 1,79%, temperature factors of all particles ‘anisotropically’ refined, parameters see text]. Space group and parameters (see text) are confirmed, errors in the structure description [1] corrected. The characteristic features are shown using Extended Schlegel Diagrams of the coordination polyhedra. The Madelung Part of Lattice Energy, MAPLE, is calculated and discussed
Aziridinolysis of (Triphenylphosphazenyl)pentachlorocyclotriphosphazene X-Ray Crystal Structure of N3P3 (NPPh3 )(NC2H4)5
Authors: Kumara Swamy K. C. , Damodara Poojary M. , Krishnamurthy S. S. , Manohar H.
Published: February 2015

Reaction of aziridine with N3P3(NPPh3)Cl5 (1) affords the derivatives N3P3(NPPh3)Cl5-n(NC2H4)n (n = 1-5) whose structures are elucidated by NMR spectroscopy. The X-Ray crystal structure of N3P3(NPPh3)(NC2H4)5 shows a new conformation of the -NPPh3 group which would explain the upfield shift of the aziridino protons at the = P(NC2H4)(NPPh3)) site
Kristall- und Molekülstruktur eines [4+2]-Cycloadduktes aus 2-Methyl-1.3-benzoxaphosphol und Tetrachlor-o-benzochinon / Crystal and Molecular Structure of a Compound Formed by [4+2]-Cycloaddition from 2-Methyl-1,3-benzoxaphosphole and Tetrachlor-o-benzoquinone
Authors: Hausen Hans-Dieter , Weckler Gisela
Published: February 2015

A crystal structure determination proves that the reaction of 2-methyl-1,3-benzoxaphosphole with tetrachlor-o-benzoquinone leads to 6-methyl-benzo[h]-tetrachlorobenzo[c]-2,5,7-trioxa-1- phosphabicyclo[4.3.0]nonane via a [4+2]-cycloaddition. The possibility of an oxidative [4+1]- cycloaddition of the quinone can therefore be excluded. The compound crystallizes monoclinicly (P21/c, a = 849.9(1), b = 1009.5(2), c = 1859.4(2) pm, β = 94.03(1)°, Z = 4). The bicyclic system shows cis-configuration. In the crystalline state the endo-conformation is present
Diolefincobalt(0)-Komplexe / Diolefincobalt(0) Complexes
Authors: Klein Hans-Friedrich , Groß Joachim , Witty Hubert , Neugebauer Dietmar
Published: February 2015

Mononuclear cobalt(0) complexes containing diolefin and trimethylphosphane ligands Co(cycloocta-1,5-diene)(PMe3)2 and Co[(CH2=CHMe2Si)2O](PMe3)2 are obtained from CoCl2 by reaction with magnesium in the presence of the ligands or by substitution of cobalt(olefin)tris- (trimethylphosphane) with diolefin. Chemical and spectroscopic properties confirm the para- magnetic valence state of the compounds in solution. An X-Ray crystal structure determination of Co[(CH2=CHMe2Si)2O](PMe3)2 shows a tetrahedral arrangement of ligand functions around the cobalt atom. With butadiene a diamagnetic dinuclear complex [Co(C4H6)(PMe3)3]2 is obtained containing π-allyl co-ordination of two Co(PMe3)3 units to a linear dimer of butadiene