bluuebunny/crossref_metadata_2025 huggingface dataset:
Bis(diphenylphosphanyl)amine and its Disulfide and Diselenide. Application of the INEPT-HEED Pulse Sequence for Measurement of 1J(31P, 15N) and Isotope Induced Chemical Shifts 1⊿ 14/15N(31P) at Natural Abundance of 15N
Authors: Wrackmeyer Bernd , Garcia-Baez Efren , Zuno-Cruz Franciso J. , Sanchez-Cabrera Gloria , Rosales Maria J.
Published: February 2015

Bis(diphenylphosphanyl)amine (1), the disulfide 1S and diselenide 1Se were selected to show the efficient application of the INEPT-HEED pulse sequence for measuring coupling constants 1J(31P.15N) and isotope induced chemical shifts1⊿14/15N(31P), both at natural abundance of 15N, from 31P NMR spectra. The sign of 1J(31P,15N) (> 0) in all three compounds was determined by selective heteronuclear ]1H{31P} double resonance experiments.
Chiral Aryl Sulfonyl Hydantoins as Hypoglycemic Agents
Authors: Ahmad Roshan , Jabeen Rukhsana , Zia-ul-Haq Mohammad , Nadeem Humaira , Duddeck Helmut , Verspohl Eugen J.
Published: February 2015

Some novel chiral sulfonyl hydantoin derivatives 2a-e and 3 a-e have been prepared. p-Toluenesulfonyl chloride on treatment with L-amino acids in presence of K2CO3/H2O yielded N-(p-toluensulfonyl-)amino acids 1a - e which were cyclized in presence of NH4-SCN Ac2O to afford 1-(p-toluenesulfonyl)-5-substituted-2-thiohydantoins 2a-e. These compounds were oxidized with HNO3 to yield 1-(p-toluenesulfonyl)-5-substituted hydantoins 3a-e. The enantiomeric ratios of 3a-e were determined by 1H NMR spectroscopy using Eu(hfc)3. The antidiabetic activity of 3a-d has been determined.
A Diterpenoid with a New Modified Abietane Skeleton from Salvia palaestina
Authors: Hussein Ahmed A. , Rodríguez Benjamín
Published: February 2015

A diterpenoid, salvipalolide, possessing a new modified abietane skeleton has been isolated from Salvia palaestina. Its structure [12,14-dihy-droxy-7-oxo-2,3-seco-19(4→3)-abeo-4(18), 8,11,13- abietatetraen-2,11-olide] was established by spectroscopic means.
Crystal and Molecular Structures of the Sulfurization and Selenation Products of Bis[bis(trimethylsilyl)amino]germanium(II). Crystal Structure of (Triphenylphosphine)gold(I) Bis(trimethylsilyl)amide
Authors: Wegner Gerald L. , Jockisch Alexander , Schier Annette , Schmidbaur Hubert
Published: February 2015

Treatment of bis[bis(trimethylsilyl)amino]germanium(II) with elemental sulfur or selenium affords high yields of the corresponding monosulfide [(Me3Si)2N]2GeS and selenide [(Me3Si)2N]2GeSe, respectively. The crystalline products have now been shown to be cyclic dimers with (GeS/Se)2 four-membered rings by X-ray single crystal structure analysis. The crystal structure of (triphenylphosphine)gold(I) bis(trimethylsilyl)amide (Ph3P)Au-N(SiMe3)2 has also been determined. The molecule is a monomer with a tricoordinate nitrogen atom in a planar configuration [Si2NAu]. The compound does not undergo insertion of the bis[bis(trimethylsilyl)amino]germylene.
Synthesis and Characterization of Bromo- and Bromochloroplumbates(II). Crystal Structures of [Ph4E]2[Pb3Br8] (E = P, As) and [Ph4P][PbBrCl2] • CH3CN
Authors: Klapötke Thomas M. , Krumm Burkhard , Polbom Kurt , Rienäcker Claudia M.
Published: February 2015

[Ph4P]2[Pb3Br8] and [Ph4As]2[Pb3Br8] crystallize both in the monoclinic space group P 21/n. The lattice parameters of [Ph4P]2[Pb3Br8] are a = 14.637(7), b = 8.151(3), c = 23.388(8) Å, β = 106.02(3)°, Z = 2 and of [Ph4As]2[Pb3Br8] are a = 14.697(7), b = 8.219(3), c = 23.527(8) Å, β = 106.27(3)°, Z = 2. The lattice parameters of [Ph4P][PbBrCl2]·CH3CN, which crystallizes in the triclinic space group (P 1̅), are a = 9.435(3), b = 10.2577(14), c = 14.055(2) Å, α = 88.320(11)°, β = 84.82(2)°, γ = 84.19(2)°, Z = 2. 207Pb NMR shifts of halogenoplumbates in solution are reported.
Chemistry of Seven-Membered Heterocycles, VI. Synthesis of Novel Bicyclic Heterocyclic Compounds as Potential Anticancer and Anti-HIV Agents
Authors: Hammam Abou Elfatooh G. , El-hafeza Nagla A. Abd , Midurab Wanda H. , Mikołajczyk Marian
Published: February 2015

Several new pyridines, pyridones and pyrans fused to benzothiepine or benzoheptene ring were synthesized as potential anticancer and anti-HIV agents. The fused-ring pyridines 6. 7 and 17-19 were obtained via the reaction of the seven-membered ring ketones 1, 2 and 3 with an arylidene-malononitrile and by treatment of the ylidenemalononitriles 14, 15 and 16 with aromatic aldehydes, respectively. The corresponding pyridones 11, 12 and 13 were prepared from the ketones 1, 2 and 3 and arylmethylenecyanoacetamide. The synthesis of the fused-ring pyranes 8 and 9 involved the condensation of the ketones 4 and 5 with malononitrile under basic conditions. The rearrangement of 8 under acidic conditions gave the tetrahydropyridine 10. The pyran 20 was obtained from 15 and benzaldehyde. The screening tests showed that many of the compounds obtained exhibit good anticancer activity comparable to 5-fluorodeoxyuridine used as reference compound and moderate anti-HIV activity in comparison with AZT.
Umsetzung von N-Alkylpyridinium-Salzen mit Hydroxylamin / Reaction of N-Alkylpyridinium Salts with Hydroxylamine
Authors: Möhrle Hans , Nießen Robert
Published: February 2015

1-Methylpyridinium salts showed no reaction with excessive hydroxylamine, but nicotinic acid derivatives in HMPT gave the corresponding N-oxides. 3-Acetyl-1-methylpyridinium iodide generated the hydroximino-pyridine 1-oxide 13 and the isoxazoles 14, 15E, and 15Z. 2- and 4-Cyano-l-methylpyridinium iodides underwent no ring cleavage, but altered only the functional group. However, the 3-cyano compound was converted into the corresponding pyridine N-oxides with carboxamide, hydroxyamidine and carbaldoxime groups.
Enaminouraciles as Precursors for Synthesis of Pyrimido[4,5-a]pyrimidine- 2,4-diones
Authors: Hamama W. S.
Published: February 2015

The reaction of 6-aminouracil 1 with formaldehyde and secondary amines in ethanol at room temperature gave the corresponding 5-alkylaminomethyl derivatives (2a-c) and bis(4- pyrimidyl) methane (4). Also, Mannich reaction with primary aliphatic and aromatic amines at room temperature afforded pyrimid[4,5-d]pyrimidine (5 and 6).

Treatment of 1 with o-phenylenediamine through transamination gave com pound 7 which cyclized through intramolecular Mannich reaction with formalin to yield pyrimido[4,5-e]-[l,4]diazepine (8).
Hydratisierte Cyanoelpasolithe: Die Kristallstrukturen von (NMe4)2Li(H2O)2[Cr(CN)6] und (NMe4)2Na(H2O)[M(CN)6] (M = Cr, Co) / Hydrated Cyano Elpasolites: The Crystal Structures of (NMe4)2Li(H2O)2[Cr(CN)6] and (NMe4)2Na(H2O)[M(CN)6] (M = Cr, Co)
Authors: Schwarten Martin , Witzei Michael , Babel Dietrich
Published: February 2015

The results of single crystal X-ray structure determinations are reported for monoclinic (NMe4)2Li(H2O)2[Cr(CN)6] (a = 1736.7(2), = 888.0(1), c = 1659.3(1) p m ,β = 119.33(1)°; C2/c, Z = 4) and orthorhombic (NMe4),Na(H2O)[Cr(CN)6] (a = 960.0(2), b = 885.0(2), c = 1269.8(3) pm; Pnmm, Z = 2) and (NMe4)2Na(H2O)[Co(CN)6] (a = 1854.5(4), b = 853.5(1), c = 1328.7(3) pm; Pnma, Z = 4), the latter exhibiting a superstructure of the NaCr compound. The average distances within the hexacyano groups are Cr-C: 207.8 resp. 208.3 pm and Co-C: 189.5 pm. The alkali ions are incorporated into the elpasolite-like arrangement of the bigger ions as di- or monohydrated species [Li(H2O)2]+ and [Na(H2O)]+ resp., becoming tetrahedrally coordinated [LiO2N2] and [NaON3] within the lattice and fixed by hydrogen bridges O-H...N as well. Some structural details and relations are discussed.
N-(Halogendimethylsilyl)-1 -methylphospholanimine/N-(Halogenodimethylsilyl)-1 -methylphospholane Imines
Authors: Wolfsberger W.
Published: February 2015

N-Trimethylsilyl-1 -methylphospholane imine has been prepared by the Staudinger reaction of 1-methylphospholane with trimethylsilyl azide. Transsilylation reactions of the phosphine imine with dichloro or dibromodimethylsilane lead to dimeric N-(halogenodimethylsilyl)-l-methylphospholane imines with an ionic type of structure, containing a dicationic four-membered Si-N ring system. Upon heating, the chloro compound undergoes a reversible isomerization to give the corresponding covalent monomer.
Darstellung und magnetische Eigenschaften einiger kristalliner Nitroxidradikale/Synthesis and Magnetic Properties of Some Crystalline Nitroxide Radicals
Authors: Griesar K. , Soto-Bustamante E. A. , Haase W.
Published: February 2015

The syntheses of different nitroxide radicals are reported. The thermal behaviour of the ni­ troxide radicals was examined by polarizing microscopy, differential scanning calorimetry as well as X-ray diffraction experiments. Temperature dependent magnetic susceptibility mea­surements were carried out in order to determine the magnetic properties of these nitroxide radicals. The majority of the radicals presented here show weak antiferromagnetic exchange interactions.
Synthesis of E-9-Dodecen-1-yl Acetate Using Organomanganese Reagents
Authors: Belmar J. , Téllez J. , Baeza J. , Freer J.
Published: February 2015

The Grignard reagent obtained from 2-(6-bromohexyloxy)-tetrahydropyrane, by treatment with anhydrous manganese(II) chloride was transformed to the corresponding organomanganese reagent, which was coupled with E-1-bromo-3-hexeneby treatment with anhydrous manganese chloride. Further deprotection and acetylation furnished E-9-dodecen-1-yl acetate. A second procedure involved the coupling of E-3-hexenylmanganese bromide and 6-bromohexyl acetate. Coupling reactions were carried out at 0 °C, using tetrahydrofurane and N-methylpyrrolidone as co-solvent.
Application of High-Resolution-Magic-Angle-Spinning (HR-MAS) NMR Spectroscopy to Cosmetic Emulsions
Authors: Tseng Li-Hong , Emeis Detlef , Raitza Martin , Händel Heidrun , Albert Klaus
Published: February 2015

HR-MAS NMR spectroscopy was utilized for the characterization of three cosmetic emul­sions. The emulsions had the same chemical composition and were prepared in the same way except the homogenization step. Magic angle spinning (M A S) of the emulsions was applied to improve signal resolution by eliminating susceptibility changes as well as residual dipolar interactions within the sample. Spin-lattice relaxation times (T1) were determined according to the inversion recovery technique in the temperature range of -10 °C to 40 °C to find out phase changes of the sample ingredients. 1H and 13C NMR signals of the individual components were assigned by use of different 1D and 2D NMR experiments. The HR-MAS NMR technique offers many possibilities to further investigate samples between the liquid and the solid state.
Production of 5,7-Dihydroxy-6-hydroxymethyl-2-methoxy-1,4-naphthoquinone by the Cultured Lichen Mycobiont of Opegrapha sp. No. 9771836
Authors: Amano Takuo , Miyagawa Hisashi , Ueno Tamio , Hamada Nobuo
Published: February 2015

A new pigment was isolated from an osmotically-stressed culture of the lichen mycobiont of Opegrapha sp. and the structure was determined to be 5, 7-dihydroxy-6-hydroxymethyl-2-methoxy-1, 4-naphthoquinone by spectroscopic analyses.
Übergangsmetallkomplexe mit Schwefelliganden, 145 [1]. [Ru(NO)('pybuS4')]Br, ein Komplex mit [Ru(NO)(NS4)]-Gerüst, aktivierten CH2-Gruppen und interionischen Wechselwirkungen im Festkörper ['pybuS4'2- = 2,6-Bis(2-mercapto-3,5-di-terM>utylphenylthio) dimethylpyridin(2-)] / Transition Metal Complexes with Sulfur Ligands, 145 [1]. [Ru(NO)('pybuS4 ')]Br, a Complex with [Ru(NO)(NS4)] Core, Activated CH2 Groups, and Interionic Interactions in the Solid State ('pybuS4'2- = 2,6-Bis(2-mercapto-3,5-di-terf-butylphenylthio)dimethylpyridine(2-))
Authors: Sellmann Dieter , Häußinger Daniel , Gottschalk-Gaudig Torsten , Heinemann Frank W.
Published: February 2015

In the search for soluble and reactive ruthenium nitrosyl complexes, [Ru(NO)('pybuS4')]Br ([2]Br) was synthesized by template alkylation of NBu4[Ru(NO)('buS2')2] with py(CH2,Br)2 ['pybuS4'2-= 2,6-bis(2-mercapto-3,5-di-tert-butyl-phenylthio)dimethylpyridine(2-); 'buS2'2- = 2-mercapto-3,5-di-tert-butylphenylthiolate(2-); py(CH2Br)2 = 2,6-bis(bromomethyl)pyridine]. The solid state structure of 2 has been determined by X-ray diffraction, which reveals a head-to-head O-O interaction between the linear Ru-NO entities. The ligand CH2 protons of [2]+ are activated and exchange with D+ under ambient conditions. The ν (NO) band of [2]Br appears at 1841 cm-1 in the solid state (KBr or hostaflon mull) and is significantly blue-shifted in solution (1879 cm-1 in MeOH, 1886 cm-1 in DMF). A similar blue-shift (1866 cm-1 in KBr vs. 1888 cm-1 in MeOH) has been found for [Ru(NO)('pyS4')]Br ([1]Br) which contains the parent [Ru(NO)('pyS4')]+ cation ['pyS4'2-= 2,6-bis(2-mercaptophenylthio)dimethylpyridine(2-)]. These ν(NO) shifts can be explained either by an interionic charge-transfer between the bromide anions and the nitrosyl complex cation or by O-O interactions between two NO ligands as found for solid-state [2]Br. These interactions are not found for [1]OTs which exhibits a ν(NO) band at ca. 1890 cm-1 in the solid state (KBr, hostaflon) as well as in MeOH solution.
Darstellung und Strukturanalyse von Lithium- [tetrakis-(methylamino-)aluminat] / Preparation and Crystal Structure of Lithium[tetrakis-(methylamino-)aluminate]
Authors: Rings Sabine , Ischenko Vladislav , Jansen Martin
Published: February 2015

The preparation and spectroscopic data of the new ternary amide LiAl(NHCH3)4 are reported. The structure of the title compound has been determined from X-ray powder diffraction data (tetragonal, 141, a = 14.000(4) Å, c = 9.275(2) Å, 210 reflections, R = 3.75%, weighted R = 5.10%). Both the lithium and the aluminium atoms are coordinated tetrahedrally by nitrogen atoms. Edge-sharing pairs of lithium centered and aluminium centered tetrahedra are connected to each other in helical chains forming a 3D-framework via the remaining vertices. A comparison of the projection of the crystal structure of LiAl(NHCH3)4 along the c-axis to those of cristobalite and of hollandite, (Ba,K)2 (Mn,Fe)8O16, reveals similarities with respect to both the connectivity and the topology of ring structures.
Synthesis, Crystal Structure and Magnetic Properties of a (μ-Hydroxo)(μ-Pyrazolato) Dicopper(II) Complex
Authors: Kara H. , Elerman Y. , Prout K.
Published: February 2015

Preparation and magnetic properties of a 3,5-dimethylpyrazolate bridged binuclear copper(II) complex [Cu2(L)(3 ,5 -pyz)] (L = 1,3-Bis(2-Hydroxy-5-Chlorosalicylideneamino)propan- 2-ol) is reported. The crystal structure determined by X-ray diffraction methods. (C22H20N4O3CI2CU2), triclinic, space group P1̄, a = 9.622(3), b = 10.921(2), c = 11.420(3) Å, α = 100.73(2), β = 94.04(2), Υ = 108.08(2)°, V = 1110.2(5) Å3, Z = 2. Two copper(II) ions in a square-planar coordination are bridged via alkoxide oxygen and 3,5-dimethyl pyrozolate nitrogen atoms to form a dinuclear unit. The metal coordination sphere is four-coordinate, planar with an N2O2 donor set. The dihedral angle between the two coordination planes is 166.83°. There are significant intermolecular interactions between neighbouring binuclear entities. The shortest intermolecular Cu (1) ... Cu(1)i distance is 3.383(1) Å and the Cu(1) - O ( 1)i distance is 2.666(3) Å (i = 1 -x, -y, 1 - z). The variable-temperature magnetic susceptibility measurement for a powdered sample of the complex was carried out in the temperature range 5 - 350 K and analysed to obtain values of the parameter J in the exchange Hamiltonian ℋ = -2JScu Scu; 2J = -164 cm-1. The magnetic moment at 300 K is about 2.42 μB, and 0.22 μB at 5 K. The weak antiferromagnetism of the present complex is reasonably explained in terms of the orbital countercomplementary effect based on Hoffmann's theory for super-exchange interaction
Metal Complexes of Biologically Important Ligands, CXXV [1]. Palladium(II) and Platinum(II) Complexes of Quinine Derivatives and in vitro Tests
Authors: Hubel Roland , Jelinek Tomas , Beck Wolfgang
Published: February 2015

Several quinine substituted derivatives at the C(9)-O position (1 - 7) have been obtained from quinine and N-protected glycine chloride, chlorocarbonyl ferrocene, phenylisocyanate, dicarboxylic acid dichlorides or trimesinic trichloride. From these only the glycine derivative 1 showed significant antimalarial activity in in vitro tests against Plasmodium falciparum isolates. The quinine derivatives were used as ligands and from chloro bridged palladium and platinum complexes Cl(R3P)M(μ-Cl)2M(PR3)Cl (M = Pd, Pt) di-, tri-, tetra- and hexametallic compounds 8-21 with coordination both of the aliphatic and aromatic N-atoms were synthesized. Protection of the tertiary N atom by protonation gave the quinoline complexes 22-25. Using a stoichiometric ratio metal/ligand = 1/1 it could be shown that the coordination of metal ions at the quinoline N-atom is by far preferred. A titanium(IV) complex 36 is formulated as [Ti(quinine)3Cl]Cl3 with quinine as a zwitterionic ligand
Structural and Spectral Studies of Palladium (II) Complexes of Pyridil bis{3-Piperidyl-, bis{Hexamethyleneiminyl-, bis{N(4)-Diethyl- and bis{N(4)-Dipropylthiosemicarbazone}
Authors: Castiñeiras Alfonso , Gil Maria , Bermejo Elena , West Douglas X.
Published: February 2015

Pyridil bis{N(4)-substituted thiosemicarbazones}, in which the substituents replacing the NH2 group on the thiosemicarbazone moieties are piperidyl, H2Plpip; hexamethyleneiminyl, H2Plhexim; diethylamino, H2Pl4DE; and dipropylamino, H2PI4 DP, have been synthesized. Representative palladium(II) complexes of these bis (thiosemicarbazones) have been characterized by IR, electronic, mass, and 1H and 13C NMR spectroscopy. Crystal structures have been determined for H2Plhexim and two of its palladium(II) complexes. H2Plhexim is in the Z isomeric form with intramolecular hydrogen bonding from both thiosemicarbazone moieties to pyridine nitrogens. [Pd(Plhexim)] has square-planar N2S2 coordination (i.e., imine nitrogen and thiolato sulfur atoms). [Pd2 (Plhexim)Cl2 · DMSO has two PdNNSCl centers with the pyridine nitrogen, imine nitrogen or hydrazinic nitrogen and thiolato sulfur atoms coordinated
Synthesis, Crystal Structures and Properties of the Polychalcogenides Manganese-tris(1,2-ethanediamine)-triselenide [Mn(en)3]Se3 and Manganese-tris(1,2-ethanediamine)-monotellurodiselenide [Mn(en)3 ]TeSe2
Authors: Wendland Frank , Näther Christian , Bensch Wolfgang
Published: February 2015

The reaction of manganese(II)-chloride-tetrahydrate, caesium triselenide and elemental selenium or tellurium in 1,2-ethanediamine (en) under solvothermal conditions leads to the formation of two new isostructural compounds [Mn(en)3]Se3 (1) and [Mn(en)3]TeSe2 (2). The compounds crystallize in the orthorhombic space group Pbcn with the lattice parameters a = 1149.39(9), b = 1506.83(11), c = 935.96(6) pm for 1 and a = 1184.1(2), b = 1495.3(2), c = 949.8(1) pm for 2. Their crystal structures are built up of [Mn(en)3]2+ cations and Se3
2- or TeSe2
2- anions, respectively. Each cation is surrounded by six next neighbouring anions, and vice versa. Between the cations and the anions hydrogen bonding is observed. The thermal behaviour was investigated using differential thermal analysis, thermogravimetry as well as X-ray powder diffraction. Completely different properties were found. Compound 1 decomposes in two distinct endothermic steps, while compound 2 shows only one endothermic peak. The weight loss for 1 corresponds roughly to the emission of all en molecules, whereas the weight loss for 2 is significantly lower. The final products are composed of MnSe2 and elemental Se or Te, respectively, and an unknown crystalline phase which is different for the two samples
Silylfurane und Bis(silyl)butadiine -Synthese, Lithiumderivate, Kristallstrukturen/ Silylfurans and Bis(silyl)butadiynes - Synthesis, Lithium Derivatives, Crystal Structures
Authors: Neugebauer Peter , Klingebiel Uwe , Noltemeyer Mathias
Published: February 2015

Furan reacts with BuLi and halosilanes to give mono- (1, 5, 7), bis- (2, 6), tris- (3), and tetrakis(2-furanyl)silanes (4); (Fu-R; R = SiMe2Cl (1), SiisoPr2F (5), SitBu2F (7); Fu-R-Fu; R = SiMe2 (2), SiisoPr2 (6); Fu3SitBu (3), Fu4Si (4)), 2,5-Bis(silyl)furans (8, 9) are obtained in the reaction of dilithiated furan and fluorosilanes in a molar ratio 1:2 (R-Fu-R; R = SiisoPr2F (8), SitBu2F (9), 1,4-Bis(di-tert-butylfluorosilyl)butadiyne (10) is formed from furan four equivalents of BuLi, and two equivalents of F2SitBu2. 10 reacts with KOH to give tBu2(OH )Si-C =C -C =C-SitBu2OH (11). Substitution of the fluorine atoms of 5 and 7 by a NH2 group occurs with MNH2 (M = Li, Na). 12 and 13 are obtained. The reaction of 13 with BuLi and tBu2SiF2 leads to the formation of FuSitBu2NHSitBu2F (14) and tBu2Si(NH-SitBu2Fu)2 (15). The lithium derivative of 14 crystallizes as monomer from THF as FuSitBu2N(LiTHF2)SitBu2F and as a dimer containing a four-membered ring (16) from n-hexane (FuSitBu2NSitBu2LiF)2 (17). The crystal structures of 4, 10, 16,17 have been determined.
Synthesis and Structure of a Tetranuclear Nickel Complex of a 40-Membered Macrocyclic Octaamine-Tetrathiophenolate Ligand
Authors: Kersting Berthold
Published: February 2015

The syntheses and characterization of tetranuclear Ni complexes [(L2)Ni4][ClO4]4 (3) and [(L2)Ni4(NCS)4] (4) of a 40-membered macrocyclic octaamine-tetrathiophenolate ligand (L2)4- are described. Single-crystal X-ray structure analysis of 4 reveals well-separated molecules of the tetranuclear isothiocyanate complex [(L2) NiII
4(NCS)4]. The four NiII centers are arranged in binuclear [N2Ni(μ2-SR)2NiN2(NCS)2] subunits containing distorted square-planar NiN2S2 and distorted octahedral NiN2S2(NCS)2 sites. The fact that the two isothiocyanate groups at the octahedral Ni site are in trans positions can be ascribed to the large ring size of the macrocycle
Condensed [PtIn3/3] and [PtIn6/6] Units as Structural Motifs in ScPtln, TbPtln, and HoPtln
Authors: Galadzhun Yaroslav V. , Zaremba Vasyl' I. , Piotrowski Holger , Mayer Peter , Hoffmann Rolf-Dieter , Pöttgen Rainer
Published: February 2015

The ternary indides ScPtln, TbPtln, and HoPtln were synthesized by reaction of the elements in an arc-melting furnace and subsequent annealing for four weeks. ScPtln and HoPtln are reported here for the first time. The three indides crystallize with the hexagonal ZrNiAl structure, a ternary ordered version of the Fe2P type, space group P6̄2m. Single crystal X-ray data yielded a = 754.6(1), c = 348.31(8) pm, wR2 = 0.0390, 177 F2 values for ScPtln, a = 759.3(1), c = 387.6(1) pm, wR2 = 0.0576, 183 F2 values for TbPtln, and a = 758.13(1), c = 381.62(1) pm, wR2 = 0.0530, 239 F2 values for HoPtln with 14 variable parameters for each refinement. Striking structural motifs of these intermetallics are short Pt-In distances (270 - 286 pm) within the three-dimensional [Ptln] polyanions which are composed of Pt(2)In6 trigonal prisms and trigonal planar P t(l)In3 units. The platinum-indium substructure of ScPtln is discussed in comparison with the various platinum-indium networks in the structures of Ptln2, Pt3In7, SrPtln, Sr2Pt3ln4, SrPtIn2, LaPtIn3, and PtIn7Fi3.
Transition Metal Complexes of Derivatized Chiral Dihydro-1,2,4-triazin-6-ones. Part III [1]. X-Ray Crystal Structure Analysis of N,N’-Bis[(1-phenyl-5-isopropyl-4,5-dihydro-6-oxo-1,2,4-triazin-3-yl)ethylidene]- propane-1,3-diamine Nickel(II)
Authors: Abushamleh Ahmad S. , El-Abadelahb Mustafa M. , Voelter Wolfgang
Published: February 2015

Template reaction of L-3-acetyl-1-phenyl-5-isopropyl-4,5-dihydro-1,2,4-triazin-6-one (lb) with 1,3-diaminopropane and nickel acetate gave the corresponding chiral complex 4 in high yield. X-ray structure determination showed that the nickel complex is square planar, and the ligand N,N’-bis[(l-phenyl-5-isopropyl-4,5-dihydro-6-oxo-1,2,4-triazin-3-yl)ethylid-ene]- propane-1,3-diamine is of tetra-aza type where the imine nitrogens and the ring HN(4) nitrogens are the coordinating sites. MS-FAB and NMR spectral data are in agreement with the X-ray structure.
Structural Investigation of Two 4-AryIhexahydro-1H,3H-pyrido[1,2-c]pyrimidine-1,3-diones
Authors: Wolska Irena , Herold Franciszek
Published: February 2015

The X-ray crystal structure determination of 4-(4'-fluorophenyl)hexahydro-1H,3H-pyrido[ 1,2-c]pyrimidine-1,3-dione (5) and 4-(4'-chlorophenyl)hexahydro-1H,3H-pyrido [1,2-c]- pyrimidine-1,3-dione (8) is reported. The crystal structures show the formation of centrosymmetric dimers via intermolecular N-H···O hydrogen bonds. The saturated ring adopts a slightly distorted sofa conformation both in 5 and in 8. In either compound the planar phenyl ring is twisted with respect to the pyrimidine-1,3-dione fragment.
3-Hexyne Complexes of M olybdenum(II) and Tungsten(II) Containing 2, 2 '-Bipyridine. X-Ray Crystal Structure of [MoI2(CO)(bipy)(η2-EtC2Et)]
Authors: Al-Jahdali Mutlaq , Baker Paul K. , Hursthouse Michael B. , Coles Simon J.
Published: February 2015

Reaction of [MI2(CO)(NCMe)(η2-EtC2Et)2] (M = Mo,W) with one equivalent of 2,2' -bipyridine (bipy) in CH2C12 at room temperature gives either the neutral complex, [MoI2(CO)(bipy)- (η2-EtC2Et)] (1) or the cationic complex, [WI(CO)(bipy)(η2-EtC2Et)2]I (2). The neutral molybdenum complex 1, has been crystallographically characterised, and has a pseudo-octahedral geometry with the iodo-ligand trans to the 3-hexyne, and with the bipy, carbon monoxide and other iodo-ligand occupying the equatorial face. 13C NMR studies show the 3-hexyne is donating four electrons to the molybdenum in 1.
Wechselwirkungen in Molekülkristallen, 160 [1,2]. Kristallzüchtung und Strukturbestimmung der verschiedenartigen Polyphenyl-Kontaktionenmultipel [p-Quaterphenylee⊖⊖][Na⊕(DME)3]2, [p-Quaterphenyl⊖⊖(Na⊕(THF)3)2] und [p-Terphenyl⊖⊖Na⊕(DME)2Na⊕(DME)]2 / Interaction in Molecular Crystals, 160 [1, 2]. Crystallization and Structure Determination of the Different Polyphenyl Contact Ion Multiples [p-Quaterphenylee⊖⊖][Na⊕(DME)3]2, [p-Quaterphenyl⊖⊖(Na⊕(THF)3)2] und [p-Terphenyl⊖⊖Na⊕(DME)2Na⊕(DME)]2
Authors: Bock Hans , Gharagozloo-Hubmann K. , Sievert M.
Published: February 2015

The π-hydrocarbons p-terphenyl and p-quaterphenyl are reduced to their dianions in aprotic solutions of different ethers at sodium metal mirrors. Single crystal structure determinations of the solvent-separated or solvens-shared contact ion multiples, [p-terphenyl⊖⊖ Na⊕(DME)2Na⊕DME]2, p-quaterphenyl⊖⊖ ][Na⊕(DME)3]2 and [p-quaterpheny⊖⊖( Na⊕(THF)3)2], prove the essential cation solvation by the chelating dimethoxyethane (DME) versus the bulky tetrahydrofuran (THF) ligands: The solution network of equilibria between solvent separated and solvent shared ion aggregates can be considerably and transparently modified by the ether solvent selected. In addition, the structures of the monomeric sodium salts reveal partly novel details of metal cation coordination by contacts Na⊕ ··· O as well as Na⊕ ··· Cπ such as in the dimeric sodium salt of p-terphenyl dianion, [(DME)2Na⊕ (terphenyl⊖⊖)(Na⊕ DME)(terphenyl⊖⊖)Na⊕ (DME)2].
Enantioselektive Gewinnung und Kristallstruktur des Ecstasy-Analogons N-Ethyl-3,4-methylendioxyamphetamin-HCl (MDE) und seiner beiden Hauptmetaboliten MDA und HME / Enantioselective Production and Crystal Structure of the Ecstasy Analogue N-Ethyl-3,4- methylenedioxyamphetamine-HCl (MDE) and its Major Metabolites MDA and HME
Authors: Büchler Jochen , Maichle-Mössmer Cacilia , Kovar Karl-Artur
Published: February 2015

A synthetic route to the production of the pure enantiomers of the ecstasy-analogue N-Ethyl- 3,4-methylenedioxyamphetamine (MDE) and its major metabolites MDA and HME is presented. The crystal and molecular structure of these compounds has been determined by X-ray crystallography. The hydrogen bonding in the crystal lattice is examined and significant differences were found by comparing (R)- and (S)-MDA-HCl.
Synthesis, Crystal Structure and Magnetic Properties of a Novel GdIII -CuII Heterodinuclear Complex
Authors: Kara H. , Elerman Y. , Prout K.
Published: February 2015

Preparation, crystal structure and magnetic properties of a heterodinuclear complex, LCu(Me2CO)Gd(NO3)3 (L = (N,N′-bis(3-methoxysalicylidene)propane- 1,2-diamine) are reported. The crystal structure of the complex was determined by X-ray diffraction methods at 200 K. (C19H22N2O4 )Cu(C3H6O)Gd(NO3)3, monoclinic, space group P21/c, with a = 9.795(9), b = 18.763(3), c = 15.579(2) Å , β = 95.297(2) V = 2850.9(7) Å3 and Z= 4. The central region of the complex is occupied by Cu(II) and Gd(III) ions which are bridged by two phenolato oxygen atoms of the ligand. The copper ion adopts a square-based 4+1 coordination mode, the equatorial N2O2 donors being afforded by the ligand while the axial position is occupied by an oxygen atom of the acetone molecule. The Gd(III) ion is deca-coordinated. In addition to the two phenolate oxygen atoms, the coordination sphere contains two oxygen atoms of the OMe side arms of L and six oxygen atoms from the three bidentate nitrate ions. The Gd... Cu separation is 3.425(3) Å and the dihedral angle between the GdO(l)Cu and GdO(2)Cu planes is 164.8°. The magnetic susceptibility of the complex was measured over the range 5 - 350 K and the observed data were successfully simulated by the equation based on the spin-Hamiltonian operator (H = -JSCu · SGd), giving the exchange integral J(Cu-Gd) = 5.6(1) cm-1. This indicates a weak ferromagnetic spin exchange interaction. The nature of the magnetic super-exchange interaction of the title compound is compared with similar [Gd(III)-Cu(II)] heterodinuclear complexes.
Photochemical Synthesis and Identification of Tetracarbonyl-bis(olefin)metal(0) Complexes of Group VI B Elements
Authors: Morkan İ. Amour , Uztetik-Morkan A.
Published: February 2015

Photolysis of hexacarbonyl metal(0) or tetracarbonyl-bis(1,3-butadiene)metal(0) (metal: chromium, molybdenum, tungsten) in the presence of tetracyanoethylene, TCNE, or fumaronitrile , FN, at room temperature yields fram-bis(μ2-tetracyano-ethylene)tetracarbonyl-chromium(0) (1), -molybdenum(0) (2), -tungsten(0) (3) and trans-bis(fumaronitrile)tetracarbonylchromium(0) (4), -tungsten(0) (5) complexes. The complexes were purified by chromatography and recrystallization and characterized by IR , 1H, 13C NMR and mass spectroscopies. It is shown that two tetracyanoethylene ligands are symmetrically bonded to the M(CO)4 moiety through their carbon-carbon double bond in the form of μ2 -TCNE . The two fumaronitrile ligands are bonded to the central atom through their nitrogen atoms. The spectral data are discussed in terms of metal → ligand π - interaction.
Wechselwirkungen in Molekülkristallen, 163 [1, 2]. Einfluß der Alkalimetall-Reduktionspotentiale auf die Bildung ihrer Kontaktionenmultipel mit Tetracen- und Decacylen-Polyanionen / Interaction in Molecular Crystals, 163 [ 1,2]. The Influence of Alkaline Metal Reduction Potentials on the Formation of their Contaction Multiples with Tetracene and Decacyclene Polyanions
Authors: Bock Hans , Gharagozloo-Hubmann K. , Holl S. , Sievert M.
Published: February 2015

The reduction of selected π-hydrocarbons tetracene and decacyclene by various alkaline metals allowed the crystallization and structure determination of the following five solvent separated or solvent shared contaction multiples: [Tetracene⊖⊖ (Na⊕Diglyme)2], [Tetracene⊖⊖ - (K⊕ Triglyme)2], [Decacyclene• ⊖] [Cs⊕ (Triglyme)2], [Decacyclene•⊖⊖⊖] [Na⊕ (DME)3]3, [Decacyclene⊖⊖⊖⊖ (K⊕Diglyme)4]. These alkaline salts contain a radicalanion M• ⊖ , dianions M⊖⊖ , a radicaltrianion M•⊖⊖⊖ , and a tetraanion M⊖⊖⊖⊖ generated by single or multiple electron transfer. Their structures are discussed in terms of the difference in alkaline metal reduction potentials, the powerful cation solvation, the effects of the anion charges and of the cation radii. Further aspects concern the solvent-shared or solvent-separated cation coordination to the anions, the polyion aggregation and for the radical trianion the experimentally proven and quantumchemically simulated Jahn/Teller distortion. Altogether the investigation adds facets to the knowledge of multielectrontransfer reactions and of selforganisation phenomena of alkaline salts.
Monosubstituierte Derivate des Halbsandwich-Komplexes Cp*Ta(CO)4 - Vergleich mit den analogen Vanadiumverbindungen Cp*V(CO)3L und Röntgenstrukturanalyse des γ-Picolin-Komplexes Cp*V(CO)3(NC5H4-Me(4)) / Monosubstituted Derivatives of the Halfsandwich Complex Cp*Ta(CO)4 - Comparison with the Analogous Vanadium Compounds Cp*V(CO)3L and X-Ray Structural Analysis of the γ-Picoline Complex Cp*V(CO)3(NC5H4-Me(4))
Authors: Herberhold Max , Frohmader Gudrun , Peukert Jürgen , Milius Wolfgang
Published: February 2015

The photo-induced substitution of a CO ligand in Cp*Ta(CO)4 (1) has been used to prepare a series of Cp*Ta(CO)3L (2) complexes, in which the two-electron ligand L includes, e.g., isonitriles, sulfanes, cyclic ethers, phosphanes and pyridines. The complexes (2a-y) were characterized by their v(CO) frequencies and their 1H and 13C NMR spectra, and were compared - if possible - with the corresponding vanadium complex, Cp*V(CO)4 (3) and its derivatives, Cp*V(CO)3L (4). The molecular structure of the 4-picoline complex Cp*V(CO)3(NC5H4-Me(4)) (4r) has been determined by X-ray crystal structure analysis.
Triterpenes from Mimusops elengi
Authors: Jahan Nusrat , Malik Abdul , Afza Nighat , Choudhary M. Iqbal , Shahzad-ul-Hassan S.
Published: February 2015

Two new triterpenes, 3β,19α,23-trihydroxy-urs-12-ene (1) and 3β-(p-hydroxy-c/s-cinnamoyloxy) urs-12-en-28-oic acid (2) have been isolated from the methanolic extract of Mimusops elengi along with 3β-(p-hydroxy-trans-cinnamoyloxy)urs-12-en-28-oic acid (3), which has been obtained for the first time from this species, and ursolic acid (4), respectively. Their structures were established through chemical and spectral studies. Compounds (3) and (4) were found to exhibit potent inhibitory activity against α-glucosidase enzyme.
Studies with 2-Arylhydrazono-3-oxopropanaIs: A Novel Route to 4-Aroyl-2-aryl-1,2,3-triazoIes, 3-Substituted 4-Arylazopyrazoles, 2-Substituted Glyoxalonitrile and 3-Oxoalkanonitriles
Authors: Abdel-Khalik Mervat Mohammed , Agamy Samia Michel , Elnagdi Mohammed Hilmy
Published: February 2015

2-Arylhydrazono-3-oxopropanals 1 react with hydroxylamine hydrochloride to yield the corresponding oximes 3 that are cyclized into isoxazoles 9 on reflux in acetic anhydride and are converted into 2-arylhydrazono-3-oxonitriles (4) on treatment with pyridine. The reaction of 1 with hydrazines afforded dihydrazones 10 which were converted to arylazopyrazoles 11 when treated with pyridine, whereas treatment with an acidic reagent resulted in the formation of 3-aroyl-2-phenyl-l,2,3-triazoles 12.
Metallradien, Ionenradien und Wertigkeiten fester metallischer Elemente / Metallradien, Ionenradien und Wertigkeiten fester metallischer Elemente
Authors: Trömel Martin
Published: February 2015

Metallic radii rm are correlated with the ionic radii ri by linear relationships. For groups 1 up to 7 as well as for AI, Ga, In, Tl, Sn, and Pb the ionic radii refer to the maximum valences (oxidation states) as known from compounds according to rm ≈ 1.16 • (ri + 0.64) [Å], For groups 8 up to 12, rm ≈ 0.48 · (ri + 2.26) [Å] with valences W = 14 -G (G = group number). These valences are considered regular (Wr). For groups 1 up to 12, they obey the equation Wr = 7 -[G -71]. According to this equation all outer s electrons and the unpaired d electrons should be involved in chemical bonding, i.e. in the cohesion of the element in the solid state. From the melting temperatures and the atomic volumes it is concluded, however, that only 19 out of the 30 d-block elements have regular valences, namely the elements of groups 3, 5, 6, 10, 11 as well as Os, Ir, Zn, Cd, and possibly Ru. All of the non-regular valences are lower than the regular ones. Four of them are integers: Mn 3; Fe, Co 4; Re 6.
A Diazenidoborate: Formation and Structure of Cs[(CF3)3BN=NCF3]
Authors: Brauer D. J. , Bürger H. , Chebude Y. , Pawelke G.
Published: February 2015

Cs[(CF3)3BNH2] reacts with CF3NO to form cesium trans-trifluoromethyldiazenido-tris(trifluoromethyl) borate Cs[(CF3)3BN=NCF3] (2), the structure of which has been investigated by single-crystal X-ray diffraction. The diazene nature of the anion is confirmed by the length of the N=N bond, 1.231(6) Å, and the size of the N-N-B angle, 115.5(4)° - the B-N bond length being 1.559(7) A. Compound 2 is hitherto the first diazenidoborate which has been fully characterized
The Crystal Structure of Bi3Se4Br
Authors: Petasch U. , Söhnel T. , Oppermann H. , Eggenweiler U. , Keller E. , Krämer V.
Published: February 2015

The crystal structure of Bi3Se4Br has been determined. With respect to its (Bi,Se) substructure it is related to orthorhombic Bi2Se3 and to Bi19S27Br3
A Conformational Study of 5,10,15,20-Tetraalkyl-22H+,24H+-porphyrindiium Salts (Dication Salts)
Authors: Senge Mathias O.
Published: February 2015

N-protonation of 5,10,15,20-tetraalkylporphyrins with n-butyl, isobutyl, isopropyl, 1-ethyl-propyl or tert-butyl substituents yields the respective 22,24-dihydroporphyrins (22H+,24H+-porphyrindiium salts) that exhibit highly nonplanar conformations. Depending on the steric demand of the meso substituents, the free base porphyrins have planar to moderately ruffled macrocycles (primary or secondary alkyl residues) or are severely ruffled (tertiary alkyl resi­dues). X-ray crystallographic studies show that protonation of porphyrins with n-Bu (2), i-Pr (3) or EtPr (4) substituents leads to steric congestion of the core resulting in symmetric, saddle distorted macrocycles as evidenced by average displacements of the Cb positions from the mean plane ranging from 0.79 to 1.01 Å. The structures observed for these porphyrin diacids are very similar in distortion mode and degree of nonplanarity to 5,10,15,20-tetraaryl-22H+,24H+-porphyrindiium salts and to 2,3,7,8,12,13,17,18-octaalkyl-5,10,15,20-tetraaryl-porphyrins. In contrast, protonation of the highly ruffled 5,10,15,20-tetrakis(teA-r-butyl)porph-yrin results in a switch of the conformational distortion mode. The dication 6 shows both saddle distortion (Cb displacements -1.3 Å) and ruffling of the macrocycle (Cm displacements of approx. 0.48 Å). Thus, the need to accomodate four N-H units in the porphyrin core with its associated out-of-plane tilting of the pyrrole rings and the steric strain induced at the meso carbon atoms results in a highly nonplanar porphyrin with mixed distortion modes.
High-spin Cyclopentadienyl Complexes, Part 7. Ambivalent Interpretation of the Bonding in Iron-Copper Complexes: Metalated Arene versus Carbocyclic Carbene
Authors: Wallasch Mark W. , Vollmer Guy Y. , Kafiyatullina Alsu , Wolmershäuser Gotthelf , Jones Peter G. , Mang Markus , Meyer Wilfried , Sitzmann Helmut
Published: February 2015

The electron distribution within a mesityl ligand bridging a cyclopentadienyliron fragment attached to the mesityl π system and a second metal fragment connected to the ipso carbon of the mesityl ring has been probed using a copper(I) halide as a component in [CpmFe (μ,η5 :η1-C6H2Me3)CuCl] (2) and its copper bromide derivative 3. This approach minimizes steric effects and allows for DFT calculations the results of which are in very good agreement with structural data. The calculations show a significant carbene character already for the bare phenyl anion as a result of electrostatic repulsion of the lone pair pushing the π electrons away from the ipso carbon towards the para carbon atom of the aromatic ring. π Coordination of a cyclopentadienyliron(II) fragment to the phenyl anion to form a hypothetical sandwich complex does not change this situation. The iron center rather follows the unsymmetric distribution of π charge with an unsymmetrical coordination to the π system. Coordination of a copper(I) chloride moiety to the phenyl anion or to the hypothetical π complex [CpFe(C6H5)] in both cases equally lowers that carbene character by attracting the lone pair of the ipso carbon and thus decreasing its repulsive influence on the π electrons.
Reactivity of Triethylborane towards Di(alkyn-1-yl)(chloro)silanes. Competition between 1,1-Organoboration and 1,2-Hydroboration
Authors: Khan Ezzat , Bayer Stefan , Wrackmeyer Bernd
Published: February 2015

Reactions of di(alkyn-1-yl)(chloro)silanes, HSi(Cl)(C≡C-R)2, R1Si(Cl)(C≡C-R)2 or HSi(Cl)-(C≡C-R)C≡C-Rʹ, with an excess of triethylborane, BEt3, proceed slowly (several days) at 100 -120 °C. Twofold 1,1-organoboration of HSi(Cl)(C≡C-R)2 or HSi(Cl)(C≡C-R)C≡C-Rʹleads tosiloles, independent of R = nBu, tBu, SiMe3. This provides the most straightforward way to silolesbearing both a hydrogen and a chlorine at the silicon atom. However, in the cases of R = Ph, BEt3 actsas 1,2-hydroborating reagent in the intermolecular first step of the reaction, leading to 1-silacyclobutene derivatives. All siloles and 1-silacyclobutene derivatives were characterized by multinuclear NMR spectroscopy (1H, 11B, 13C and 29Si). Comparable 1-silacyclobutene derivatives were formed using 9-borabicyclo[3.3.1]nonane, 9-BBN, as a well established 1,2- hydroborating reagent
Di(phosphavinyl) Ethers (2,4-Diphospha-3-oxapentadienes)
Authors: Birzoi Roxana M. , Bugnariu Delia , Goers Christine , Guerrero Gimeno Rafael , Gust Thorsten , Riecke Antje , Benkõ Zoltán , Könczöl László , Nyulászi László , Wismach Cathleen , Jones Peter G. , Schmutzler Reinhard , Bartsch Rainer , Mont Wolf-W. du
Published: February 2015

Hydrolytic cleavage of the P-chlorophosphaalkenes (RMe2Si)2C=PCl (R = Me: 1a; R = iPr: 1b) in the presence of triethylamine leads to di(phosphavinyl) ethers (2,4-diphospha-3-oxapentadienes) [(RMe2Si)2C=P]2O (2a, 2b) as main products, accompanied by alkylphosphinic acids (RMe2Si)2(H)CP(H)(O)OH (3a, 3b). The hydrolysis of (PhMe2Si)2C=PCl (1c) proceeds less selectively. Reactions with metal oxides under aprotic conditions provide 2a [impure, from 1a with (nBu3Sn)2O] and 2b [from iodophosphaalkene (iPrMe2Si)2C=PI with Ag2O] as oils. 1H, 13C, 29Si and 31P NMR spectra, however, allow unambiguous characterisation of 2a and 2b. Formation mechanisms, structure, and C=P-O π stabilisation of the oxabisphosphaalkene [(H3Si)2C=P]2O (2ʹ) were studied with DFT methods. The double [2+4] cycloaddition reaction of 2a with two equivalents of cyclopentadiene leads to the phosphinous anhydride 7 as a mixture of diastereomers whereas the addition of two equivalents of tetrachloro-o-benzoquinone proceeds in a diastereoselective fashion. An X-ray crystal structure determination of the resulting oxo-bridged bis(2-phospha-2,5-dioxa-3,4-benzophospholene) derivative 8 revealed the presence of a racemic mixture of (R,R)- and (S,S)-configurated molecules. The solid state structure of a by-product, bisylphosphonic tetrachlorocatechol monoester (Me3Si)2CH-P(=O)(OH)-o-OC6Cl4OH 9, was also determined crystallographically.
Übergangsmetall- und Lanthanoid-Komplexe von 1,4,7,10-Tetraallylund 1,4,7,10-Tetra-3-butenyl-1,4,7,10-tetraazacyclododecan
Authors: Schumann Herbert , Kuse Katharina , Hummert Markus , Pickardt Joachim
Published: February 2015

1,4,7,10-Tetraazacyclododecane (1) reacts with allylbromide and 3-butenylbromide giving 1,4,7,10-tetraallyl-1,4,7,10-tetraazacyclododecane (TAC) (2a) and 1,4,7,10-tetra-3-butenyl-1,4,7,10- tetraazacyclododecane (TBC) (2b), respectively. Compounds 2a and 2b react with FeCl2, CoCl2, RhCl3, NiCl2, CuBr2, and TmCl3 forming the complexes [FeCl(TAC)]Cl (3a), [FeCl(TBC)]Cl (3b), [CoCl(TAC)]Cl (4), [RhCl(TAC)]Cl2 (5), [NiCl(TAC)]Cl (6a), [NiCl(TBC)]Cl (6b), [CuBr(TAC)]Br (7), [TmCl(TAC)]Cl2 (8a), and [TmCl(TBC)]Cl2 (8b). The reaction of 6a with an excess of CuCl affords a coordination polymer in which [NiCl(TAC)]+ cations are connected by [Cu6Cl8]2−
anions (9). The 1H and 13C NMR spectra of 2a, 2b, 5, and 6a, as well as the single crystal X-ray structures of 2a ・3HCl, 6a, 6b, 7, and 9 are reported and discussed.
Synthesis and Reactions of 5-[Amino(thiomethyl)methylene]- 2,2-dimethyl-1,3-dioxane-4,6-dione
Authors: Al-Sheikh Ahmad , Sweidan Kamal , Maichle-Mößmer Cäcilia , Steimann Manfred , Kuhn Norbert
Published: February 2015

5-[Amino(thiomethyl)methylene]-2,2-dimethyl-1,3-dioxane-4,6-dione (4) is obtained from 5-[bis- (thiomethyl)methylene]-2,2-dimethyl-1,3-dioxane-4,6-dione (1) and aqueous ammonia in excellent yield. Its reaction with m-chloroperbenzoic acid gives the sulfoxide derivative 5-[amino(sulfinylmethyl) methylene]-2,2-dimethyl-1,3-dioxane-4,6-dione (5). With triphenylphosphine, 5 reacts to give triphenyl( thiomethyl)phosphonium 5-cyano-2,2-dimethyl-1,3-dioxane-4,6-dionate (6) from which the methyltriphenylphosphonium salt 6a is obtained with excess triphenylphosphine. The crystal structures of 4, 5 and 6a are discussed.
Synthesis, Structure and Reactions of 1,3-Dimethyl-5-bis(thiomethyl)methylenebarbituric Acid
Authors: Sweidan Kamal , Abu-Rayyan Ahmed , Al-Sheikh Ahmad , Maichle-Mößmer Cäcilia , Steimann Manfred , Kuhn Norbert
Published: February 2015

1,3-Dimethyl-5-bis(thiomethyl)methylenebarbituric acid (8) is obtained from 1,3-dimethylbarbituric acid and CS2/NEt3 followed by alkylation with methyl iodide. Compound 8 reacts with aqueous ammonia to give 5-amino(thiomethyl)methylene-1,3-dimethylbarbituric acid (9). With benzylamine, the thiomethyl substituent in 9 is replaced to give 5-amino(benzylamino)methylene-1,3- dimethylbarbituric acid (10) while with methanesulfonic acid the sulfonate salt 11 is formed. The crystal structures of 8 and 9 are reported.
Configurational Flexibility of Epimeric β-Aminothioether-chelated Ruthenium(II) η6-Arene Complex Salts
Authors: Weber Immo , Heinemann Frank W. , Bauer Walter , Zenneck Ulrich
Published: February 2015

Five chiral β -aminothioethers were obtained via different routes orientated on literature protocols. Three of these β -aminothioethers were reacted with two di-μ-chloro-bis{chloro[η6-arene]- ruthenium(II)} derivatives, resulting in the title complex salts. The complex cations exhibit three stereocenters, viz. ruthenium and sulfur atoms and the chiral benzylic carbon atom of the chelate ligand backbone. Both, ruthenium and sulfur stereocenters epimerize into a mixture of four NMR distinguishable diastereomers in equilibrium, but the designed chiral benzylic carbon atom is stable under all conditions applied so far. The relative diastereomer concentrations in solution depend mainly on the spatial requirements of the η6-arene ligand rather than on the thioether moiety. Diastereomer ratios and the absolute configurations in solution were studied by NMR and CD spectroscopy. The spectroscopic results fit to the absolute X-ray crystal structure parameters determined for the diastereomers present in the crystalline state.
Synthesis and Crystal Structure of the Triple-decker Complex [(η5-C5Me5)- Ru(μ,η5-1,3-C3B2Me5)RhCl- (Ph2PCH2)2]
Authors: Nie Yong , Oeser Thomas , Siebert Walter
Published: February 2015

The dimer [(η5-C5Me5)Ru(C3B2Me5)RhCl]2 (2) reacts with 1,2-bis(diphenylphosphino)ethane (dppe) to give the triple-decker complex [(η5-C5Me5)Ru(C3B2Me5)Rh- (dppe)Cl] (3). Its constitution follows from NMR and MS data, and a single-crystal X-ray diffraction study.