bluuebunny/crossref_metadata_2025 huggingface dataset:
Synthesis, Crystal Structure and Antiproliferative Activity of 6-Adamantyl-3-aryl[1,2,4]triazolo[3,4-b][1,3,4]thiadiazoles
Authors: Khan Mahmood-ul-Hassan , Akhtar Tashfeen , Yasin Khawaja A. , Al-Masoudi Najim A. , G. Jones Peter G. , Hameed Shahid
Published: February 2015

A series of 3,6-disubstituted [1,2,4]triazolo[3,4-b][1,3,4]thiadiazoles 5a - l bearing an adamantyl moiety were synthesized by condensation of 4-amino-5-aryl-2H-1,2,4-triazole-3(4H)-thiones 4a -l with adamantyl-1-carboxylic acid in the presence of POCl3. The structures of the newly synthesized compounds were established using spectroanalytical techniques and verified further by the crystal structure determination of compounds 5a and 5j. The compounds were screened for their antiproliferative activity against a large panel of human cell lines.
Enantioselective Synthesis of a 2,2-Disubstituted Tetrahydro-3- benzazepine as Novel NMDA Receptor Antagonist
Authors: Husain Syed Masood , Fröhlich Roland , Schepmann Dirk , Wünsch Bernhard
Published: February 2015

The tricyclic oxazolidines trans-4 and cis-4 were interconverted upon treatment with allyltrimethylsilane/ TiCl4. The oxazolidine trans-4 was diastereoselectively reacted with PhMgBr to yield the 4,4-disubstituted 3-benzazepinone 6, along with two side products. An X-ray crystal structure analysis of 6 proved the (R)-configuration of the stereogenic center C-4 and thus the retention of configuration. Reduction of 6 with AlCl3/LiAlH4 (1/3) followed by hydrogenolysis with H2, Pd/C resulted in the formation of enantiomerically pure 2-methyl-2-phenyl-tetrahydro-3-benzazepine 11 which has a moderate affinity (Ki = 496 nM) to the PCP binding site of the NMDA receptor.
Ring-opening Addition Reactions of 1-tert-Butoxycarbonyl-3,4- epoxypiperidine with Amine Nucleophiles
Authors: Poojary Boja , Hee-Jong Lim
Published: February 2015

Ring-opening addition reactions of 1-tert-butoxycarbonyl-3,4-epoxypiperidine leading to the formation of the corresponding regioisomeric trans-β -aminoalcohols were carried out with three different types of amine nucleophiles under different reaction conditions with a view to study the reactivity and regioselectivity.
Bond Activation in Iron(II) and Nickel(II) Complexes of Polypodal Phosphanes
Authors: Gentschow Simon-Andreas , Kohl Stephan W. , Bauer Walter , Heinemann Frank W , Wiedemann Dennis , Grohmann Andreas
Published: February 2015

A pyridine-derived tetraphosphane ligand (donor set: NP4) has been found to undergo remarkably specific C-P bond cleavage reactions, thereby producing a ligand with an NP3 donor set. The reaction may be reversed under suitable conditions, with regeneration of the original NP4 ligand. In order to investigate the mechanism of this reaction, the NP3 donor ligand C5H3N[CMe(CH2PMe2)2][CMe2(CH2PMe2)] (11) was prepared, and its iron(II) complex 4 generated from Fe(BF4)2 ・6H2O, with methyl diethylphosphinite (7) as an additional monodentate ligand. Ligand 11 has, in addition to the NP3 donor set, one methyl group in close contact with the iron center, reminiscent of an agostic M・ ・ ・H-C interaction. Depending on the stoichiometric amount of iron(II) salt, a side product 15 is formed, which has a diethylphosphane ligand instead of the phosphinite 7 coordinated to iron(II). While attempts to deprotonate the metal-coordinated methyl group in 4 were unsuccessful, the reaction was shown to occur in an alternative complex (18), which is similar to 4 but has a trimethylphosphane ligand instead of the phosphinite 7. The reaction of complex 15 with CO gave two different products, which were both characterized by single-crystal X-ray diffraction. One (19) is the dicarbonyl iron(II) complex of the triphosphane ligand 11, the other (3) is the carbonyl iron(II) complex of the tetraphosphane C5H3N[CMe(CH2PMe2)2]2 (1). This suggests an intermolecular mechanism for the C-P bond formation in question.
Structural Properties of Ruthenium Biimidazole Complexes Determining the Stability of their Supramolecular Aggregates
Authors: Rockstroh Nils , Peuntinger Katrin , Görls Helmar , Guldi Dirk M , Heinemann Frank W. , Schäfer Bernhard , Rau Sven
Published: February 2015

The results of a detailed investigation of the influence of substituents in a variety of ruthenium biimidazole-type complexes [Ru(R-bpy)2(R´-bi(bz)imH2)]2+ (R = H, tBu; R´ = H,Me; bi(bz)imH2 = 2,2´-bi(benz)imidazole) on selected structural and photophysical properties is reported. The photophysical properties are only marginally influenced by the substituents at the bipyridine and the biimidazole core. All complexes show intense absorptions in the visible range of the spectrum with maxima around 475 nm, and emission from the formed excited state occurs at wavelengths between 650 and 670 nm. The comparison of structural properties determined by X-ray analysis within a series of related complexes shows that the Ru-N bond lengths to the coordinated bipyridines are not significantly influenced by the substituents, but slight differences in the Ru-N bond lengths to the biimidazole-type ligands can be detected. The reactions between ruthenium complexes containing different biimidazole-type ligands with the sulfate dianion, however, show a strong correlation between the substituents at the biimidazole core and the solubility of the product. The bibenzimidazolecontaining complexes precipitate from aqueous solution whereas the ruthenium complex containing unsubstituted biimidazole stays in solution. The solid-state structure of one example of the sulfatecontaining products (2b) shows that strong hydrogen bonds between the secondary amine function of the bibenzimidazole and the oxygen functionalities of the sulfate contribute to this unexpected behavior.
Fluorescent Nano pH Indicators Based on Supramolecular Interactions
Authors: Langhals Heinz , Pust Tim
Published: February 2015

Lipophilic pH-sensitive perylene derivatives were combined with detergents in a supramolecular arrangement to obtain nanomicelles that can be applied as fluorescent pH indicators for the aqueous phase.
Synthesis and Characterization of the Heptanuclear [MnIII
6 CoIII]3+ Triplesalen Complex: Evidence for Exchange Pathways Involving Low-spin CoIII
Authors: Krickemeyer Erich , Hoeke Veronika , Stammler Anja , Schnack Jürgen , Bögge Hartmut , Glaser Thorsten
Published: February 2015

The reaction of the tert-butyl-substituted triplesalen ligand H6talent-Bu2 with MnII(OAc)2・ 4H2O and K3[CoIII(CN)6] results in the formation of the heptanuclear complex [{(talent-Bu2 )- (MnIII(MeOH))3}2{CoIII(CN)6}](PF6)2(OAc)・11MeOH ([MnIII
6 CoIII](PF6)2(OAc)・11MeOH, 1 ・11MeOH), which has been characterized by FT-IR spectroscopy, elemental analysis, ESI-MS, single-crystal X-ray diffraction, and magnetic measurements. The molecular structure of the [MnIII
6 CoIII]3+ complex is closely related to the already published analogs [MnIII
6CrIII]3+ and [MnIII
6 FeIII]3+. Variable-temperature variable-field and μeff vs. T magnetic data have been analyzed in detail by full-matrix diagonalization of the appropriate spin-Hamiltonian consisting of isotropic exchange, zero-field splitting, and Zeeman interaction, taking into account the relative orientation of the D tensors. This allowed a careful inspection of the MnIII-MnIII exchange interaction involving a diamagnetic central metal ion. A satisfactory reproduction of the magnetic data required the incorporation not only of an exchange interaction between the MnIII ions belonging to one triplesalen half unit, but also of an exchange coupling between MnIII ions belonging to different triplesalen subunits. Satisfactory reproduction of the experimental data has been obtained for the parameter set J1 = −(0.50±0.04) cm−1, J2 = +(0.05±0.02) cm−1, and D = −(2.5±0.5) cm−1. A detailed analysis of the J1 coupling taking into account the molecular structures of the three available heptanuclear complexes [MnIII
6MIII]3+ (M = Cr, Fe, Co) indicates that the exchange interaction between the MnIII ions belonging to the same triplesalen subunit involves not only an exchange pathway through the central phloroglucinol unit but also an exchange pathway through the central metal ion.
Isolation and X-Ray Characterization of {[Phthalazinium](CuCl2)}∞: ANew Example of a Dichlorocuprate(I) Presenting aRare Staircase Chain Structure
Authors: Plasseraud Laurent , Cattey Hélène , Richard Philippe
Published: February 2015

Air-sensitive complexes [Cu2(μ-phtz)3(PR3)2][CF3SO3]2 (phtz = C8H6N2), 3 (R = phenyl) and 4 (R = benzyl) have been synthesized from {[Cu(CF3SO3)]2・C6H5Me} (1) at room temperature, in acetonitrile solution, after successive additions of stoichiometric amounts of phthalazine (phtz) and triphenylphosphine and tribenzylphosphine, respectively. The dissolution of 4 in an excess of benzyl chloride gave rise to the slow formation of orange needles, characterized by an X-ray crystallographic analysis as the title compound, {[phthalazinium](CuCl2)}∞ (5). The solid-state structure of 5 can be described as a one-dimensional anionic chain, [(CuCl2)−]∞, presenting a rare staircase shape with terminal chloride ligands. The negative charges are compensated by monoprotonated phthalazinium cations [phtzH]+ which are stacked through π-π interactions between N-heterocyclic rings, and are also in N-H hydrogen bonding interaction with the terminal chloride ligands of the anionic chain. The formation of 5 was unexpected and can be explained by the dechlorination of benzyl chloride molecules.
Enantiomerically Pure C2-symmetric Dinuclear Silver(I) and Copper(I) Complexes from a Bis(2,2´-bipyridine)-substituted 9,9´-Spirobifluorene Ligand
Authors: Piehler Torsten , Lützen Arne
Published: February 2015

We have prepared a new bis(bipyridyl) ligand 1 based on a chiral 9,9´-spirobifluorene core in both enantiomerically pure forms. This ligand was found to undergo diastereoselective self-assembly to optically pure dinuclear coordination compounds upon coordination to copper(I) and silver(I) ions. Surprisingly, however, the resulting diastereomer was not found to be D2-symmetric which is usually found for similar bis(bidentate) ligands, but rather C2-symmetric with differently configurated metal centers.
Mono- and Di-Lanthanide Derivatives of 19-Tungsto-2-Arsenate(III)
Authors: Ismail Amal H , Bassil Bassem S , Römer Isabella , Redeker Nils C. , Kortz Ulrich
Published: February 2015

Two types of lanthanide-containing derivatives of the 19-tungsto-2-arsenate(III) [As2W19O67- (H2O)]14− (As2W19) have been synthesized in mildly acidic aqueous media and characterized in the solid state. The ytterbium(III)-containing anion [Yb(H2O)2K(H2O)2As2W19O67(H2O)]10− (1) was formed by reaction of Yb3+ with the potassium salt of As2W19, while the lanthanum(III) derivative [La2(H2O)6As2W19O67(H2O)]8− (2) was formed by reaction of La3+ with the sodium salt of the trilacunary precursor [B-α-AsW9O33]9− (AsW9). The polyanions 1 and 2 crystallize as hydrated salts in the triclinic system, space group P1̄: K9.5Na0.5[Yb(H2O)2K(H2O)2As2W19O67(H2O)]·25H2O (KNa-1) with cell dimensions a = 12.4730(5), b = 17.4630(9), c = 21.1990(10) Å, α = 72.568(3)◦, β = 85.442(2)◦, γ = 89.147(3)◦, Z = 2; Na8[La2(H2O)8As2W19O67(H2O)]·17H2O (Na-2) with cell dimensions a = 14.929(2), b = 17.769(3), c = 20.754(4) Å, α = 77.203(10)◦, β = 80.273(9)◦, γ = 72.670(9)◦, Z = 2. Both compounds KNa-1 and Na-2 were characterized in the solid state by FTIR spectroscopy, TGA and single-crystal X-ray diffraction analyses. In polyanion 1, the As2W19 unit sandwiches one ytterbium and one potassium ion leading to a structure with idealized Cs symmetry, whereas polyanion 2 incorporates two lanthanum ions leading to a structure with idealized C2v symmetry. Compositional analogs of polyanions 1 (Ln = La, Ce, Eu, Gd and Lu) and 2 (Ce) were also synthesized and identified by FTIR spectroscopy.
Microspectroscopic Analysis of the X-Ray-induced Photoreduction in Fe- and Mn-containing SMMs
Authors: Schmidt Norman , Scheurer Andreas , Sperner Stefan , Fink Rainer H.
Published: February 2015

Scanning transmission X-ray microspectroscopy (STXM) and L-edge near-edge X-ray absorption fine structure (NEXAFS) spectroscopy have been applied to study the valence states of metal ions in various Fe- and Mn-containing single-molecule magnet materials, in particular the ligand-stabilized metal complexes NaFe6 (so-called “ferric wheel”), Fe4 (so-called “ferric star”) and Mn7 (so-called “manganese wheel”).We compare dose-dependent L-edge absorption spectra with the results of theoretical studies of the involved metal ions to conclude on the change in oxidation state upon increasing the X-ray dose. It is found that even low-intensity irradiation induces the reduction of the weakly interacting metal ions, and that the soft X-ray-induced photoreduction is less pronounced in microcrystalline films.
Secondary Interactions in Crystals of all Ten Isomers of Di(bromomethyl)naphthalene
Authors: Jones Peter G. , Kuś Piotr
Published: February 2015

The packing of all ten isomers of di(bromomethyl)naphthalene is analysed; nine of the structures were determined here, one (the 1,8-isomer) was already known. The 1,5- and 2,6-isomers display crystallographic inversion symmetry and the 2,7-isomer mirror symmetry through the central bond. For the 1,2-, 1,7- and 2,7-isomers, the bromomethyl groups point to the same side of the ring system, and for all other isomers to opposite sides. As expected, the molecules are linked into aggregates by various types of interactions: weak hydrogen bonds CH...Br, Br...Br interactions, CH...π contacts, π...π stacking and Br...π contacts. The weak hydrogen bonds tend to be numerous but relatively long, and do not combine to form readily recognisable patterns; a more readily assimilated view of the packing is based on the Br...Br interactions, which are observed for all isomers except 1,7 and 2,3, and in some cases lead to aggregation to form quadrilaterals or chains. With decreasing frequency, the interactions π...π, C-H...π and Br...π are observed, but the latter are rare (just two examples) and very asymmetric, with contacts to only one or two carbons.
Synthesis and Site-selective Metalation of a Benzene-o-dithiol/ Pyridylimine Ligand
Authors: Dömer Johannes , Pape Tania , Hahn F. Ekkehardt
Published: February 2015

The benzene-o-dithiol/pyridylimine (S-S)/(N-N) ligand H2-7, representing the first example of a new type of bis(bidentate) heterodonor ligands with a mixed donor set, has been synthesized by Schiff base condensation of pyridine-2-carbaldehyde with an amine-substituted benzene-o-dithiol moiety. Bis(cyclopentadienyl)titanium dichloride reacts selectively at the S-S donor group of H2-7 to yield complex [Cp2Ti(7)].
Crystal and Molecular Structure of 3-(N-Methoxy-N-methylcarbamoyl)- 2,2,5,5-tetramethyl-1-oxy-pyrroline
Authors: Frey Guido D. , Herdtweck Eberhardt
Published: February 2015

The crystal structure of the stable nitroxide radical 3-(N-methoxy-N-methylcarbamoyl)-2,2,5,5- tetramethyl-1-oxy-pyrroline was determined from single-crystal X-ray data: orthorhombic, space group Pbca (no. 61), a = 9.0213(1), b = 12.8625(1), c = 21.2406(2) Å, V = 2464.68(4) Å3 and Z = 8. The adjacent molecules assemble to a supramolecular layer structure in the solid state, linked by two intermolecular C-H...O hydrogen bonds.
Synthesis and Structural Characterization of Diisopropylammonium Trifluoroacetate and Diisoproplyammonium Pentafluoropropionate
Authors: Reiß Guido J. , Meyer Michaela K.
Published: February 2015

Diisopropylammonium trifluoroacetate ({[iPr2NH2][CF3COO]}; dip tfa; 1) and diisopropylammonium pentafluoropropionate ({[iPr2NH2][C2F5COO]}; dip pfp; 2) have been synthesized and structurally characterized by X-ray diffraction and spectroscopic methods. Both compounds form hydrogen-bonded cyclic dimers (Etter symbol: R4
4 (12)) in the solid state. The asymmetric unit of 1 contains one trifluoroacetate anion and one dip cation in the centrosymmetric space group Pī. The asymmetric unit of 2 consists of two crystallographically independent pentafluoropropionate anions and two independent dip cations forming dimers in the form of rings, both lying around centers of symmetry in the space group Pī. In dip tfa and dip pfp the cations act as double hydrogen bond donors, and each of the two oxygen atoms of the carboxyl group are single hydrogen bond acceptors. The donor acceptor distances of the N-H...O hydrogen bonds are within the expected range for medium strong hydrogen bonds. The quasi-molecular cyclic dimers are connected with neighboring units only by van der Waals interactions.
1H NMR Studies on the Cation Motions in Crystalline Cadmium Bromide Complexes [C(NH2)3]Cd2Br5, [(CH3)3NH]3Cd2Br7, and [i-C3H7NH3]CdBr3
Authors: Ishihara Hideta , Horiuchi Keizo , Furukawa Yoshihiro
Published: February 2015

1H NMR T1 measurements of crystalline [C(NH2)3]Cd2Br5 showed a single minimum due to the C3 reorientation of the planar [C(NH2)3]+ ion with an activation energy (Ea) of 35.8 kJ mol−1. In [(CH3)3NH]3Cd2Br7 crystals, two T1 minima appeared which are assigned to the C3 reorientation of methyl groups in the [(CH3)3NH]+ cation with Ea = 13.0 kJ mol−1 and to the C3 reorientation of a whole cation around the molecular C3 axis with Ea = 28.9 kJ mol−1. In [i-C3H7NH3]CdBr3 crystals, a very broad T1 minimum appeared near 160 K which is assigned to the C3 reorientations of two methyl groups with Ea = 11.3 kJ mol−1 and of an NH3 group with Ea = 13.3 kJ mol−1 in the [i-C3H7NH3]+ ion, and another minimum with Ea = 23.5 kJ mol−1 near 300 K assigned to a higher order molecular motion of the cation.
Acridone Alkaloids and Coumarins from the Stem Bark of Citropsis articulata (Rutaceae)
Authors: Meva’a Luc Mbaze , Songue Jules Lobe , Wansi Jean Duplex , Waffo Alain François Kamdem , Dongo Etienne , Mpondo Théophile Ngando , Sewald Norbert
Published: February 2015

A new acridone alkaloid, citropsine A (1), and thirteen known compounds (2 - 14) were isolated from the MeOH extract of the stem bark of Citropsis articulata. Structures of all compounds were determined by detailed analyses of their 1D and 2D NMR spectra, mass spectrometric data and by comparison with previously known analogs.
1,3-Dialkyl-5-hydroxy-2-thioxoimidazolidin-4-one / 1,3-Dialkyl-5-hydroxy-2-thioxoimidazolidin-4-ones
Authors: Kuhn Norbert , Maichle-Mößmer Cäcilia , Steimann Manfred , Walker Isabel , Zeller Klaus-Peter
Published: February 2015

The 1,3-dialkyl-5-hydroxy-2-thioxoimidazolidin-4-ones 8 (R = Me, Et, iPr) were obtained from the corresponding thiourea and glyoxylic acid monohydrate in very good yield. Their reactions with chlorotrimethylsilane in the presence of triethylamine gave the 1,3-dialkyl-5-trimethylsiloxy-2-thioxoimidazolidin- 4-ones 9. NMR and crystal structure data of 1,3-diisopropyl-5-hydroxy-4-thioxoimidazolidin-4-one (8c) have confirmed the acyloin-type structure of the above mentioned compounds.
The New Niobium Cluster Azides (NH4)4[Nb6Cl12(N3)6](H2O)2 and Na1.15(3)La0.85(3)[Nb6Cl12(N3)6](H2O)13(1). Syntheses and Crystal Structure Determination
Authors: Reckeweg and Olaf , Simon Arndt
Published: February 2015

The cluster compounds (NH4)4[Nb6Cl12(N3)6](H2O)2 (1) and Na1.15(3)La0.85(3)[Nb6Cl12(N3)6]- (H2O)13(1) (2) have been synthesized by the reaction of an aqueous solution of Nb6Cl14 with an excess of NaN3 and the respective chloride salts. 1 crystallizes isotypically to the other alkali metal cluster azides in the space group P1̄̄ (no. 2) with the lattice parameters a = 908.97(8), b = 932.78(8), c = 1045.78(9) pm; and α = 95.94(1), β = 101.68(1) and γ = 102.41(1)°, while 2 is found to be nearly isostructural to the alkaline earth metal cluster azides crystallizing in the space group Fd3̄m (no. 227) with the lattice parameter a = 1996.9(1) pm. The stoichiometry of 2 was confirmed by EDX analyses which also led to a reconsideration of the water content of alkaline earth metal cluster azide compounds. The title compounds and results obtained from the reevaluation of the alkaline earth metal cluster azides are compared.
Synthesis and Characterization of Fluorescent Polyoxometalate Nano-/Microrods
Authors: Shen Yan , Peng Jun , Chen Changyun , Chen Dan , Zhang Huanqiu , Meng Cuili
Published: February 2015

Fluorescent nano-/microrods of the polyoxometalate (POM) K4H[Eu(α-SiW11O39)- (H2O)2] ・ 17H2O were obtained in aqueous solution by a conventional synthesis method. The nano-/microrods have been characterized by elemental analysis and FT-IR, UV/Vis, and TG-DTA data, and their morphology was examined by ESEM-FEG, showing that the average ratio of diameter to length is 1 : 20. The obtained nano-/microrods exhibit a regular profile and an intense fluorescence.
Sesterterpenes from the Sponge Dysidea sp.
Authors: Yang Xiaoxia , Shao Zhiyu , Zhang Xingqun
Published: February 2015

The acetone extract of the sponge Dysidea sp. was subjected to chromatography techniques for fractionation and purification. A new sesterterpene, scalarester (1), and four known scalaranes, viz. scalarin (2), scalaradial (3), desacetylscalaradial (4), and desacetoxyscalaradial (5), were obtained. Their structures have been elucidated by means of spectroscopic data interpretation, mainly 1D and 2D NMR and mass spectrometry.
Synthesis and Crystal Structure of Barium Indide Ba9In4
Authors: Smetana Volodymyr , Simon Arndt
Published: February 2015

A new binary compound in the system Ba-In has been synthesized and structurally characterized. According to singlecrystal X-ray diffraction data Ba9In4 crystallizes with tetragonal symmetry (I4/m, a = 13.948(2), c = 5.888(1) Å, V = 1145.5(3) Å3, Z = 2, R1 = 0.037, wR2 = 0.071). The very moisture-sensitive compound could be obtained as single phase by reaction of metallic barium and indium at 350 °C.
Metal Complexes of Biologically Important Ligands, CLXXV [1]. Pentamethylcyclopentadienyl Halfsandwich Complexes of Rhodium(III) and Iridium(III) with Schiff Bases from 2-(Diphenylphosphino)- benzaldehyde and α-Amino Acid Esters
Authors: Schreiner Bernhard , Wagner-Schuh Barbara , Beck Wolfgang
Published: February 2015

The reactions of the chlorido-bridged complexes [Cp*M(Cl)(μ-Cl)]2 (M = Rh, Ir) with Schiff bases (P-N-O) from 2-(diphenylphosphino)benzaldehyde and α-amino acid esters afford the complexes Cp*M(Cl)2(P-N-O) in which the ligands function as monodentate P donors (M = Ir) or as bidentate P-N donors (M = Rh). These complexes can be converted into cationic complexes [Cp*M(Cl)(P-NO)]+ with bidentate P-N ligands by treatment with NH4PF6. The cationic complexes [Cp*M(Cl)(PN- O)]+Cl− have been detected also in solutions of Cp*M(Cl)2(P-N-O). The P-N-coordinated complex [Cp*Rh(Cl)(Ph2P-C6H4-C(H)=N-C(H)(CH2Ph)CO2Me)]+PF6
− was characterized by X-ray diffraction. From Cp*M(Cl)2(P-N-O) and AgBF4 or AgPF6 (molar ratio 1 : 2) the dicationic complexes [Cp*M(P-N-O)]2+ are formed in which the ester group is also coordinated to the metal atom. The Schiff base from 2-(diphenylphosphino)benzaldehyde and allylglycine ester acts as a tridentate ligand, however with coordination of the C=C allyl group instead of the ester function.
π-Spacer-coupled Diimidosulfinates
Authors: Schulz Thomas , Dauer David-Raphael , Stalke Dietmar
Published: February 2015

To synthesize ligands that are capable of coordinating two metals, 1,4-dilithiumbenzene and 4,4´-dilithiumbiphenyl were reacted with different sulfurdiimides to give coupled diimidosulfinates. [(THF)4Li2{(NSiMe3)2S}2biphenyl] (1) and [(THF)1.5Li2{(NSiMe3)2S}2biphenyl]∞ (2) could be isolated and structurally characterized. While 1 forms distinct molecules in the solid state, 2 crystallizes in infinite chains. The lithium complex with a benzene group as spacer could not be isolated due to co-complexed lithium bromide. Subsequent metal exchange reactions with dimethylaluminum chloride afforded [{Me2Al(NtBu)2S}2biphenyl] (3) and [{Me2Al(NSiMe3)2S}2(C6H4)] (4).
A New Limonoid fromTrichilia connaroides
Authors: Geng Zhao-Liang , Fang Xin , Di Ying-Tong , Zhang Qiang , Shen Yue-Mao , Hao Xiao-Jiang
Published: February 2015

A new limonoid, trichiliton B (1), was isolated from the twigs and leaves of Trichilia connaroides. Its structure was elucidated on the basis of spectroscopic analyses, including application of ESI-MS, HR-ESI-MS, UV, IR, 1D and 2D NMR techniques
Abietane Diterpenoids and a Lignan from Pinus yunnanensis
Authors: Feng Tao , Cai Xiang-Hai , Tan Qin-Gang , Luo Xiao-Dong
Published: February 2015

Two new abietane diterpene acids, pinyunins A (1) and B (2), a new lignan, 2-[2-hydroxy-5-(3- hydroxypropyl)-3-methoxyphenyl]-1-(2,3-dihydroxyphenyl)propane-1,3-diol (3), and eight known diterpenoids (4 - 11) were isolated from the bark of Pinus yunnanensis Franch. Their structures were elucidated by spectroscopic methods. Compounds 1 - 3 exhibited high inhibitions on Cox-2 (> 80 %) and low inhibitions on Cox-1 (< 50%), showing the trend of selective inhibition of Cox-2, while the positive controls NS-398 (Cox-2) and SC-560 (Cox-1) gave inhibitions of 97.09% and 61.30 %, respectively. Compounds 1 - 11 were evaluated for their cytotoxicity against five human cancer cell lines with Cisplatin as a positive control.
The Structure of the Product Formed by Condensation of Malononitrile with Dialkyl Acetone-1,3-dicarboxylates
Authors: Šimunek Petr , Baškovč Jernej , Grošelj Uroš , Meden Anton , Svete Jurij , Stanovnik Branko
Published: February 2015

By the condensation of malononitrile (1) with dialkyl acetone-1,3-dicarboxylates 2a, b alkyl (3- cyano-6-alkoxy-2-oxo-1,2-dihydropyridin-4-yl)acetates 6a, b are formed in contrast to an earlier report according to which diethyl 3-(dicyanomethylene)glutarate 3b was obtained in the reaction of 1 and 2a. Compounds 6a, b were transformed with DMFDMA into the corresponding (E)-alkyl 2-(3- cyano-6-alkoxy-2-oxo-1,2-dihydropyridin-4-yl)-3-(dimethylamino)propenoates 7a, b. The structures of 6a and 7a were confirmed by X-ray structural analysis.
Parallel Solution-phase Synthesis of (2S,4E)-4-(Arylaminomethylidene)pyroglutamic Acids
Authors: Svete Jurij , Grošelj Uroš , Baškovč Jernej , Dahmann Georg , Stanovnik Branko
Published: February 2015

A library of twelve N(4´)-substituted di-tert-butyl (2S,4E)-4-arylaminomethylidene-5-oxopyrrolidine-1,2-dicarboxylates 6/6´a - l were prepared in 47 - 90% yield by parallel acid-catalysed treatment of di-tert-butyl (2S,4E)-4-[(dimethylamino)methylidene]-5-oxopyrrolidine-1,2-dicarboxylate (4) with anilines 5a - j, ethyl glycinate (5k), and ethyl β -alaninate (3l). Acidolytic deprotection of compounds 6a - c, e - j afforded the corresponding (2S,4E)-4-arylaminomethylidene-5-oxopyrrolidine-2-carboxylic acids 7a - c, e - j in 39 - 99% yield. The configuration around the C=C double bond in the enaminones 6 and 7 was determined by NMR spectroscopy.
2-Isoxazolinium Salts and 3-Isoxazolines: Exploratory Chemistry and Uses for the Synthesis of Branched Amino Polyols and Amino Acids
Authors: Jäger Volker , Frey Wolfgang , Bathich Yaser , Shiva Sunitha , Ibrahim Mohammad , Henneböhle Marco , LeRoy Pierre-Yves , Imerhasan Mukhtar
Published: February 2015

2-Isoxazolines represent a well known class of heterocycles, readily accessible in particular by 1,3-dipolar cycloaddition of nitrile oxides to alkenes. 2-Isoxazolines are easily transformed into 2- isoxazolinium salts by N-methylation, and further into 3-isoxazolines by deprotonation. In contrast to the parent system, less is known concerning the chemistry of the derived classes, and potential applications in synthesis. - 2-Isoxazolinium salts, due to their iminium part, are prone to the attack of nucleophiles, and examples for this, addition of hydride (reduction) and C-nucleophiles like methylmagnesium bromide, cyanide, methane nitronate, and malonate are given. With these adducts, syntheses of β - and α-amino acids with OH-containing side chains have been effected. The cyanide products also are useful as precursors of branched, unsymmetrical 1,2-diamino polyols. - On the other hand, 3-isoxazolines due to their oxy-enamine part, represent species with nucleophilic sites and therefore react with electrophilic reagents. Examples given are [3+2] cycloadditions with nitrile oxides, [2+2] cycloadditions with dimethyl acetylenedicarboxylate, and [2+1] cycloaddition in the form of epoxidation which, however, led to a dihydro-1,3-oxazine nitrone by initial attack at the nitrogen atom, in an unprecedented oxidation/N-dealkylation/rearrangement sequence.
Chemistry of Polyhalogenated Nitrobutadienes, Part 9: Acyclic and Heterocyclic Nitroenamines and Nitroimines from 2-Nitroperchlorobuta-1,3-diene
Authors: Zapol’skii Viktor A. , Namyslo Jan C. , Gjikaj Mimoza , Kaufmann Dieter E.
Published: February 2015

Various amino, diamino, aminothio, or benzotriazolo compounds derived from the exceedingly versatile 2-nitroperchlorobutadiene (1) gave structurally interesting and physiologically promising nitro-enamines, -imines, -amidines, and hydrazines as well as ring closure reaction products, e. g. pyrimidines and pyrazoles. Most of these reactions turned out to be highly selective with good to very good yields. The structure of the pyrazole precursor (E,E)-1-(benzotriazol-1-yl)-4,4-dichloro-3- (4-ethoxyphenylamino)-1-(4-ethoxyphenylimino)-2-nitrobut-2-ene (30), due to its exceptional substitution pattern, was evidenced by single-crystal X-ray diffraction analysis.
Reduction of Dipyrido Ureas via 6-Alkyloxydipyrido[1,2-c;2´,1´-e]imidazolium Salts
Authors: Kunz Doris , Deißler Christine , Gierz Verena , Rominger Frank , Oeser Thomas
Published: February 2015

Dipyrido uronium salts can readily be synthesized by alkylation of dipyrido ureas with Meerwein’s reagent. Compared to the corresponding ureas, the uronium salts are more reactive towards basic or reducing agents like metal hydrides. Reactivity studies show that the uronium salts can react as alkylating agents towards DMSO, DBU and NaOEt along with release of the respective dipyrido ureas. In contrast, reduction of the dipyrido uronium salts with sodium borohydride or sodium trimethoxyborohydride in dry and degassed acetonitrile leads to the imidazolium salts 7a and 7b in moderate yields. Analysis of the by-products reveals an in situ carbene formation which can be reversed by using degassed but wet acetonitrile as solvent. The yield of 7b was increased significantly by these means.
Synthese und Kristallstrukturen von N-[ω-(Dimethylammonio)alkyl]- N´,N´,N´´,N´´-tetramethylguanidinium-chlorid-tetraphenylboraten / Synthesis and Crystal Structures of N-[ω-(Dimethylammonio)alkyl]-N´,N´,N´´,N´´- tetramethylguanidinium Chloride Tetraphenylborates
Authors: Tiritiris Ioannis , Lissner Falk , Schleid Thomas , Kantlehner Willi
Published: February 2015

Dicationic N,N´,N´,N´´,N´´-pentasubstituted guanidinium dichlorides 4a, b are obtained from the chloroformamidinium salt 2 and diamines 3a, b. N-[2-(Dimethylammonio)ethyl]-N´,N´,N´´,N´´-tetramethylguanidinium chloride tetraphenylborate (5a) and N-[3-(dimethylammonio)propyl]-N´,N´,N´´,N´´-tetramethylguanidinium chloride tetraphenylborate (5b) were synthesized from 4a, b by anion metathesis with one equivalent of sodium tetraphenylborate. The thermal properties of the salts 5a, b were studied by means of DSC methods, and their crystal structures were determined by single-crystal X-ray diffraction analysis. For 5a a solid-solid phase transition is observed at −156 ◦C to a low-temperature structure. The room-temperature modification (α-5a) crystallizes in the centrosymmetric orthorhombic space group Pbca (a = 13.1844(4), b = 13.8007(4), c = 34.7537(11) A° ).

The guanidinium ions are interconnected via chloride ions through bridging N-H· · ·Cl hydrogen bonds, providing isolated units. The tetraphenylborate ions show some dynamic disordering in the crystal structure. The low-temperature modification (β -5a) also crystallizes orthorhombically, but in the non-centrosymmetric space group Pna21 (a = 13.1099(4), b = 69.1810(11), c = 13.5847(5) A° ) and consists of four crystallographically independent cations and anions in the unit cell. Compared with the room-temperature structure, a similar N-H· · ·Cl hydrogen bond pattern is observed in the β -phase, but the tetraphenylborate ions are now completely ordered. 5b crystallizes in the monoclinic space group P21/c (a = 10.8010(3), b = 14.1502(5), c = 20.9867(9) A° , β = 94.322(1)◦). In the crystal structure the guanidinium ions are linked via chloride ions through N-H· · ·Cl hydrogen bonds, but in contrast to 5a two infinite strands are formed along the a axis with the tetraphenylborate ions interspersed between them for charge compensation.
Hydrothermal Sintering under Mild Temperature Conditions: Preparation of Calcium-deficient Hydroxyapatite Compacts
Authors: Yanagisawa Kazumichi , Kim Jae-Hyen , Sakata Chisato , Onda Ayumu , Sasabe Eri , Yamamoto Tetsuya , Matamoros-Veloza Zully , Rendón-Angeles Juan Carlos
Published: February 2015

Calcium-deficient hydroxyapatite (CDHA) prepared by the coprecipitation method was solidified by the hydrothermal hot-pressing technique, and compacts of CDHA with high bulk density beyond 80% were obtained at 200 ℃. Each reaction parameter, viz. reaction temperature, pressure, and time, was systematically changed from the standard conditions to investigate its effects on density, Vickers hardness, and Ca/P ratio of the compacts obtained. The reaction temperature and pressure had a large effect on densification, but not the reaction time because the densification proceeds in a short time. The densification by hydrothermal hot-pressing involved dissolution and precipitation of the starting CDHA powder, so that the Ca/P ratio changed from 1.52 of the starting powders to 1.61 of the compact obtained by hydrothermal hot-pressing at 200 ℃ and 35 MPa for 24 h with the addition of 10 wt.-% water
Hydrothermal Synthesis, Crystal Structure and Catalytic Properties of a Novel Polyoxometalate: (C5H7N2)3(AsMo12O40) ·2C5H6N2 · 1.5H2O
Authors: Cai Tie-Jun , Shen Xiao-Ming , Peng Zhen-Shan , Lu Shu-Zi , Deng Qian
Published: February 2015

(C5H7N2)3(AsMo12O40)・2C5H6N2・1.5H2O was hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. Crystal data: monoclinic, P21/n, a = 13.310(3), b = 22.399(5), c = 19.820(4) A° , β = 99.99(3) ◦, V = 5819(2) °A3, Z = 1, wR(F2) = 0.1345. The structure consists of Keggin-type [AsMo12O40]3− polyoxoanions. The title compound has a high catalytic activity for the oxidation of acetone tested in a continuous-flow fixed-bed micro-reactor. When the initial concentration is 5.3 g m−3 in air and the flow rate is 2.5 mL min−1, the acetone is completely eliminated at 150 ◦C.
Synthesis and Structural Aspects of Two Trinuclear Cyano-bridged Heterometallic Complexes with Monodentate Coordination of Perchlorate and Acetate Anions
Authors: Datta Amitabha , Pillet Sébastien , Chuang Nien-Tsu , Lee Hon Man , Huang Jui-Hsien
Published: February 2015

Two new cyano-bridged trinuclear heterometallic complexes [Ca2(phen)4(ClO4)(H2O)3- Fe(CN)6]・H2O (1) and [Ca2 (phen)4(CH3COO)(H2O)3Fe(CN)6]・2H2O (2) (where phen = 1,10- phenanthroline) have been synthesized and characterized by single-crystal X-ray diffraction techniques, IR spectroscopy and thermogravimetric analysis. The structure of complex 1 features a central [Fe(CN)6]3− unit that links a monocation [Ca(phen)2(H2O)(ClO4)]+ and a dication [Ca(phen)2- (H2O)2]2+ via two trans cyanide bridges. Similarly, complex 2 also features a central [Fe(CN)6]3− unit that links a monocation [Ca(phen)2(H2O)(CH3COO)]+ and a dication [Ca(phen)2(H2O)2]2+ via two trans cyanide bridges. In 1 and 2, both Ca centers are seven-coordinated and achieve a pentagonal- bipyramidal geometry whereas the Fe center in both the complexes possesses a distorted octahedral geometry. Intra- and intermolecular hydrogen bonding networks are present in 1 and 2 that impart the overall molecular stability to both the systems.
Synthesis, Structure and Characterization of a Novel Two-Dimensional Supramolecular Mn(II) Coordination Polymer Constructed from a 1,10-Phenanthroline Derivative and a Flexible Dicarboxylate
Authors: Kong Zhi-Guo , Ma Xiao-Yuan , Xu Zhan-Lin
Published: February 2015

The title complex, [Mn2(glu)(L)2(HL)2]・0.5H2O (H2glu = glutaric acid, HL = 2-(2-chloro-6-fluorophenyl)-1Himidazo[ 4,5-f][1,10]phenanthroline) has been synthesized using a hydrothermal method and characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. Crystal data: C162H88Cl8F8Mn4N32O9, triclinic, space group P1¯, a = 14.932(5), b = 16.414(5), c = 17.891(5) Å , α = 115.851(5), β = 91.288(5), γ = 112.894(5)◦, V = 3536.4(19) Å3, Z = 1. Compound 1 exhibits 1D chains which are further stacked by C-H...π interactions to give two-dimensional supramolecular layers.
PbO / PbF2 Flux Growth of YScO3 and LaScO3 Single Crystals – Structure and Solid-State NMR Spectroscopy
Authors: Balamurugan Sarkarainadar , Rodewald Ute Ch. , Harmening Thomas , Wüllen Leo van , Mohr Daniel , Deters Heinz , Eckert Hellmut , Pöttgen Rainer
Published: February 2015

Well-shaped small single crystals of the orthorhombic perovskites YScO3 and LaScO3 were grown from mixtures of the corresponding sesquioxides RE2O3 in PbO/PbF2 fluxes. Both structures were refined from single-crystal diffractometer data: GdFeO3-type, Pnma, a = 570.68(7), b = 789.3(1), c = 542.44(7) pm, wR2 = 0.0363, 448 F2 values for Y0.96ScO2.94, and a = 579.68(9), b = 810.3(2), c = 568.3(1) pm, wR2 = 0.0387, 513 F2 values for La0.94ScO2.91, with 32 variables per refinement. The 4c rare-earth sites of both perovskites show small defects which are charge-compensated by defects on both oxygen sites, leading to the compositions La0.94ScO2.91 and Y0.96ScO2.94 for the investigated crystals. The rare-earth sites have been characterized by 89Y and 45Sc magic-angle spinning (MAS) NMR. The 45Sc quadrupolar interaction parameters extracted from these spectra by simulations are found to be in good agreement with those obtained from DFT calculations of the electric field gradient.
Synthesis, Crystal Structures and Spectroscopic Properties of RbBaTaS4 and K2BaTa2S11
Authors: Wu Yuandong , Bensch Wolfgang
Published: February 2015

Single crystals of RbBaTaS4 (1) and K2BaTa2S11 (2) were obtained from the reactions of Ta, with in situ formed fluxes of A2S3 (A = K, Rb), BaS, and S at 500 °C. Compound 1 crystallizes in the orthorhombic space group Pnma with a = 9.3286(5), b = 7.0391(4), c = 12.4365(7) Å, V = 816.6(1) Å3, Z = 4. Compound 2 crystallizes in the monoclinic space group P21/c with a = 14.5280(10), b = 12.6347(7), c = 17.5148(12) Å , β = 94.744(8)°, V = 3203.9(4) Å3, Z = 4. The structure of RbBaTaS4 (1) consists of isolated tetrahedral [TaS4]3− anions and Rb+ and Ba2+ cations. The Ba2+ cations are surrounded by nine sulfur atoms forming distorted tricapped trigonal prisms, whereas the Rb+ cations are in an irregular environment of ten sulfur atoms. The structure of K2BaTa2S11 (2) consists of two different dinuclear [Ta2S11] units which are separated by Ba2+ and K+ cations. The Ta atoms are coordinated by S2
2− and S2− ligands according to the mode [Ta2(μ2-S)(μ2-η2,η1- S2)2(η2-S2)2(S)2]4−. Each Ta atom is surrounded by seven sulfur ions forming strongly distorted pentagonal bipyramids. The two [TaS7] polyhedra share a common face in the [Ta2S11] unit. The K+ and Ba2+ cations are statistically distributed over the crystallographic sites. Compound 2 has also been characterized by UV/Vis diffuse reflectance, IR and Raman spectroscopy
From a Dissymmetrical Oxamidate Ligand to a 2D Coordination Polymer: Synthesis, Crystal Structure and Magnetic Properties
Authors: Liu Bao Lin , Dang Juan , Zang Shuang Quan , Wang Qing Lun , Tao Ruo Jie
Published: February 2015

A new dissymmetrical oxamidate ligand has been used to construct a metal-organic network. Using this ligand, a novel coordination polymer, namely {[Cu(obea)]2Cu・CH3OH・H2O}n (1) [H3obea = N1-(2-carboxyphenyl)-N2-(2-hydroxyethyl)oxalamide] has been synthesized and characterized by single-crystal X-ray analysis. The structure of complex 1 consists of neutral trinuclear complex units. Through syn-anti carboxylate bridges, the complex features a 2D structure with a helical substructure. Its magnetic properties have been investigated.
An Air-induced Synthesis of a Salt [AuCl2(DDDT)](MET-TTF) (DDDT = 5,6-Dihydro-1,4-dithiin-2,3-dithiolate, MET-TTF = Bis(methylthio)ethylenedithiotetrathiafulvalene)
Authors: Yang Wei , Ren Zhi-Gang , Bian Guo-Qing , Zhu Qin-Yu , Dai Jie
Published: February 2015

Reaction of Au(PPh3)Cl with MET-TTF in the presence of air resulted in a new charge-transfer salt [AuCl2(DDDT)](MET-TTF) (1, DDDT = 5,6-dihydro-1,4-dithiin-2,3-dithiolate, MET-TTF = bis(methylthio)ethylenedithiotetrathiafulvalene). During the air-induced reaction, the Au(I) is oxidized to Au(III), while two C-S bonds in MET-TTF were cleaved simultaneously. In the crystal the radical cations in 1 are assembled into a 1D structure by intermolecular S・ ・ ・ S, S・ ・ ・C, and C・ ・ ・C contacts.
Molecular Neodymium and Yttrium Cations with the N,N-Bis[2-(pyrid-2-yl)ethyl]hydroxylaminato Ligand
Authors: Hellmann Benjamin J. , Stammler Hans-Georg , Mitzel Norbert W.
Published: February 2015

The three component reaction of LnCp3, LnCp2Cl (Ln = Nd, Y) and N,N-bis[2-(pyrid-2- yl)ethyl]hydroxylamine [HON(C2H4-o-py)2] results in the formation of the [Nd(ON(C2H4-opy) 2)2]+[NdCp3Cl]− salt in the case of neodymium and the [Y(ON(C2H4-o-py)2)2]+[YCp2Cl2]− salt if yttrium is used in the synthesis. The N,N-bis[2-(pyrid-2-yl)ethyl]hydroxylaminato ligand is able to coordinate doubly to the metal atoms resulting in the formation of a cationic species. The compounds were characterised by X-ray diffraction experiments and additionally by CHN analyses in the case of the neodymium salt.
Unprecedented Hexa- and Undecanuclear Frameworks of Two New Tin(IV) Oxo Clusters Resulting from Partial Debenzylation Reactions
Authors: Plasseraud Laurent , Cattey Hélène , Richard Philippe
Published: February 2015

A new and facile synthetic route to the known neutral cluster ((PhCH2)2SnO)6[((PhCH2)2SnOH)2- (CO3)]2 (2) as well as its reactivity toward trifluoromethanesulfonic acid (HO3SCF3, TfOH) are reported. The solid-state structure of the new solvate 2·6C7H8 has been determined by single-crystal X-ray diffraction. The core of 2 can be described as a pair of coplanar pentanuclear [(PhCH2)2SnO]5 ladders bridged at their ends by two carbonate groups. Successive additions of TfOH to a suspension of 2 in CD3CN were monitored by 119Sn{1H} NMR spectroscopy showing the transformation of the fingerprint of 2 (δ = −244, −246, −306 ppm), via new upfield signals, to a final broad resonance located at δ = −474 ppm. Thereafter, two unprecedented ionic monobenzyltin(IV) oxo clusters, 3 and 4, resulting from a debenzylation reaction and exhibiting unusual hexa- and undecanuclear frameworks, respectively, have been isolated as single crystals.
Synthesis and Crystal Structure of AgTl3(Cr2O7)2
Authors: Dietrich Volker , Pitzschke Dragan , Jansen Martin
Published: February 2015

Red single crystals of AgTl3(Cr2O7)2 were prepared via high oxygen pressure synthesis as well as by hydrothermal autoclave techniques. Initially, AgTl3(Cr2O7)2 was obtained from a reaction of stoichiometric mixtures of Ag2O, Cr and TlNO3 under elevated oxygen pressures. Following an optimized approach, the title compound can be synthesized at mild hydrothermal conditions, starting from AgNO3, TlNO3 and K2Cr2O7 in aqueous solution. AgTl3(Cr2O7)2 crystallizes in space group C2/c (no. 15) with a = 10.3638(3), b = 10.4817(3), c = 13.4717(4) Å , β = 106.55(1)°, V = 1402.80(5) Å3, and Z = 4. The structure refinement was based on 3554 independent reflections and resulted in R1 = 2.13 %, wR2 = 4.54 %. The crystal structure contains independent Cr2O7
2− anions, which are surrounded by silver and thallium cations forming layers that are stacked perpendicular to the bc plane.
Glycosides from Cephalaria Species
Authors: Halay Erkan , Kırmızıgül Süheyla
Published: February 2015

Three novel triterpene glycosides (1 - 3), namely lycicoside I, II and cilicicoside I, were isolated from two different Cephalaria (Dipsacaceae) species along with one known oleanane- and one iridoit- type of glycoside. The structures of these compounds were established as 3-O-[β -D-glucopyranosyl( 1→3)-α-L-rhamnopyranosyl(1→4)-β -D-xylopyranosyl(1→4)-β -D-xylopyranosyl]-28-O-[β -Dglucopyranosyl( 1→6)-β -D-glucopyranosyl]-oleanolic acid (1), 3-O-[β -D-xylopyranosyl(1→3)-α- L-rhamnopyranosyl(1→4)-β -D-xylopyranosyl]-28-O-[β -D-glucopyranosyl]-oleanolic acid (2) from Cephalaria lycica Matthew and 3-O-{β -D-glucopyranosyl(1→4)-β -D-xylopyranosyl(1→3)-α-Lrhamnopyranosyl( 1→2)-[β -D-glucopyranosyl(1→3)]-α -L-rhamnopyranosyl}-28-O-[β -D-glucopyranosyl( 1→6)-β -D-glucopyranosyl]-hederagenin (3) from Cephalaria cilicica Boiss. & Kotschy, on the basis of spectroscopic methods (1D and 2D NMR techniques, mass spectrometry) and chemical evidence. In addition, three new prosapogenins, 1B - 3B, were obtained from the basic hydrolysis of 1 - 3. The antimicrobial activity of 1 - 3 was tested against some Gram-positive and Gram-negative bacteria strains.
Daphlongamines I and J. New Yuzurine-type Alkaloids from Daphniphyllum longeracemosum
Authors: Li Chun-Shun , Di Ying-Tong , Guo Jie , Zhang Qiang , Hao Xiao-Jiang
Published: February 2015

Two new Yuzurine-type Daphniphyllum alkaloids, daphlongamines I and J (1, 2), were isolated from the fruits of Daphniphyllum longeracemosum. Their structures were established by spectroscopic methods, especially 2D NMR techniques
OnemoreCompound Containing the CBN4- Ion – Synthesis, Single-crystal Structure and Vibrational Spectra of Ca15(CBN)6(C2)2F2
Authors: Reckeweg Olaf , Schulz Armin , Di Salvo Francis J.
Published: February 2015

Single crystals of Ca15(CBN)6(C2)2F2 were obtained by the reaction of graphite, hexagonal BN and CaF2 with an excess of distilled Ca metal in silica-jacketed Ta ampoules at 1300 K. The title compound is transparent red and crystallizes isopointal to Ca15(CBN)6(C2)2O adopting the cubic space group Ia 3̄d (no. 230, Z = 8) with the cell parameter a = 1653.6(4) pm. Its vibrational spectra are compared with IR and Raman data of similar compounds from the literature and with the newly measured Raman spectra of Ca5(BC2)(C2)Cl3 and Ca9(BC2)2Cl8.
Dimer oder nicht dimer, das ist hier die Frage: Zwei benachbarte I3
–--Ionen eingeschlossen in Hohlr¨aumen einer komplexen Wirtsstruktur
Authors: Meyer Michaela K. , Graf Jürgen , Reiß Guido J.
Published: February 2015

[Me(HO)2P-(CH2)10-P(O)OHMe]2[I3]2・MeHO(O)P-(CH2)10-P(O)OHMe (1) was synthesized and characterized by IR, Raman and NMR spectroscopy. Its structure was determined by singlecrystal X-ray diffraction (T = 100 K; space group P1̄). The structure consists of decane-1,10-diyl-bis- (methylphosphinic acid) molecules and the analogous mono-protonated cations in a ratio 1:2 connected with each other by strong O-H···O hydrogen bonds to form a two-dimensional network. Between these hydrogen-bonded layers, there are elongated cavities each containing two triiodide anions. The intermolecular I· · · I distance of the two enclosed triiodide anions is 3.6317(4) Å and should be considered as an interhalogen bonding interaction.
Fabrication and Characterization of LuminescentMultilayer Films Based on Polyoxometalates and Fuchsin Basic
Authors: Chen Changyun , Peng Jun , Shen Yan , Chen Dan , Zhang Huanqiu , Meng Cuili
Published: February 2015

A luminescent multilayer film has been fabricated from the polyoxometalate anion α- [PMo12O40]3− (α-PMo12) and the cation Fuchsin Basic (FB) through an electrostatic layer-by-layer (LbL) self-assembly method and characterized by UV/Vis spectra, atomic force microscopy and X-ray photoelectron spectra. The fluorescence properties of the LbL film have also been investigated. Cyclic voltammetry measurements have demonstrated that the electrochemical properties of the polyoxometalate and FB are maintained in the multilayer film, which exhibits electrocatalytic activity for the reduction of bromate