bluuebunny/crossref_metadata_2025 huggingface dataset:
Wechselwirkungen in Molekülkristallen, 155 [1, 2]. Kristallzüchtung und Strukturbestimmung des Radikalkation-Salzes [Tetrahydrotetrathiafulvalenium●⊕] [AlCl4
⊖]/Interaction in Molecular Crystals, 155 [1,2]. Crystallization and Structure Determination of the Radicalcation Salt [Tetrahydrotetrathiafulvalenium●⊕][AlCl4
⊖]
Authors: Bock Hans , Seibe Andreas , Sievert Mark , Havlas Zdenek
Published: February 2015

The dark red tetrahydrotetrathiafulvalenium radical cation has been generated 20 years ago by iodine oxidation of hexathia-dispiro[4.0.4.4]decane and characterized in solution by its temperature-dependent ESR spectrum. Here we report the single crystal growth of its tetrachloroaluminate salt as well as its low temperature structure determination, which proves the C=C double bond to be elongated to 140 pm length and one molecular half to be twisted by 7°. The assumed slight cyanine type distortion is supported by structural comparison with tetrakis(dimethylamino)ethene dication salts and with the 1:3 complex of tetrahydrotetrathiafulvalene mercury dichloride. Unrestricted Density Functional Theory calculations predict both the spin as well as the positive charge to be distributed predominantly within the π molecular center {S2C=CS2}.
Chemischer Transport intermetallischer Phasen, II: Das System Fe-Si/Chemical Vapour Transport of Intermetallic Phases, II: The System Fe-Si
Authors: Bosholm O. , Oppermann H. , Däbritz S.
Published: February 2015

Five phases exist in the system Fe-Si: Fe3Si, Fe2Si, Fe5Si3, FeSi, α-and β-FeSi2. All phases could be prepared by chemical transport with iodine as transport agent in the temperature range between T1 (700 °C) and T2 (1030 °C). In a attempted systematic clarification of the chemical transport reactions of all phases in the system, the effective transport equilibria were determined. Thermodynamic calculations show satisfactory agreement between calcula­tion and experiment.
Carbohydrates to Pyrano-Furanoids: New and Regioselective Palladium-Catalyzed Syntheses of Tetrasubstituted Furanoids from Carbohydrate Scaffolds
Authors: Al-Tel Taleb H.
Published: February 2015

A new strategy for the asymmetric syntheses of polysubstituted pyrano-furanoids using allylic sulfates derived from carbohydrate precursors and the dianion of diethoxycarbonyl acetone, catalyzed by Pd(0), is described.
Synthesis and Properties of Selected 4-Substituted Anhydro Sugars
Authors: Abdel-Jalil Raid J. , Saeed Muhammad , Heeg Peter , Voelter Wolfgang
Published: February 2015

A new class of 4-deoxy-4-([4-substituted-1-piperazinyl], [4-morpholinyl] and [4-(perhydrol, 4-thiazin-4-yl)])-2,3-anhydrolyxopyranosides (3a-g and 6a-g) were synthesized from epoxy triflate moities 2 and 5 and 4-substituted piperazines, morpholines and perhydro-1,4- thiazines, respectively, to test their antibacterial activity. The characterized series of new compounds was tested in vitro against E. coli ATCC11229, S. aureus ATCC6538 and C. albicans SATCC10231.
The Effect of Different Hydrogen Bonding Schemes on Melting Points of Two Isomeric 2-Hydroxy-bornane-3-carboxylic Acids
Authors: Kubicki Maciej , Borowiak Teresa , Antkowiak Wiesław Z.
Published: February 2015

The crystal structures of two isomeric compounds, 2-endo-hydroxybornane-3-endo-carboxylic acid and 2 -exo -hydroxybomane-3 -endo-carboxylic acid, have been determined by X-ray single crystal analysis. The only difference between these two compounds is the disposition of the 2-hydroxy group with respect to the bomane skeleton. Both compounds show quite different hydrogen bonding schemes. In the endo-hydroxy-endo-carboxy isomer there is one intramolecular and one intermolecular hydrogen bond, which connects molecules into infinite chains, while in the exo-hydroxy-endo-carboxy isomer there are two intermolecular hydrogen bonds that form a more stable architecture of two kinds of chains which interconnect to close rings comprising four molecules. Due to these differences the melting point of 2 is ca. 30° higher than for 1 .
Hydrogen Bonds in "Carboxyoximes": the Case of Bomane Derivatives
Authors: Kubicki Maciej , Borowiak Teresa , Antkowiak Wiesław Z.
Published: February 2015

The tendency of forming mixed carboxyl-to-oxime hydrogen bonds was tested on the series of bornane derivatives: one with the acid function only (bornane-2-endo-carboxylic acid), one with the oxime function (2,2′-diethylthiobomane-3-oxime), and one with both oxime and carboxylic functions (bornane-2-oxime-3-endo-carboxylic acid). The crystal structures of these compounds were determined by means of X-ray diffraction. In bornane-2-endo-carboxylic acid and 2,2′-diethylthiobornane-3-oxime 'homogenic' hydrogen bonds were found, and these hydrogen bonds close eight-and six-membered rings, respectively. By contrast, in bornane-2-oxime-3-endo-carboxylic acid 'heterogenic' hydrogen bonds between carboxylic and oxime bonds were found. This carboxylic-oxime, or 'carboxyoxime' system is almost always present in compounds which have both oxime and carboxylic groups; therefore it can be regarded as an element of supramolecular structures (synthon). The presence of such synthons can break the tendency of carboxylic acids and oximes towards crystallizing in centrosymmetric structures.
Synthesis and Crystal Structure of New Ternary Chalcogenides of Group IV Metals: K2ZrS4, Rb2ZrS4, and Rb2HfS4
Authors: Rumpf C. , Bensch W.
Published: February 2015

The new ternary one-dimensional chain compounds K2ZrS4 , Rb2ZrS4 and Rb2HfS4 were prepared at 350 °C by reacting A2S3 and S with elemental M (A = K, Rb; M = Zr, Hf). They are isostructural, crystallizing in the orthorhombic space group Pbca with Z = 8 . The M atoms are in a distorted octahedral environment of four S2− anions and one S2
2− unit. The structure consists of infinite anionic chains comprised of edge-sharing M S6 octahedra running parallel to the [001] direction separated by the alkali metal cations. The composition of the chain may be formulated as 1
∞[MS4/ 2 (S2)2−]. The two crystallographically independent alkali cations are in eight-and ninefold coordination of S atoms.
tBuN=V[P(SiMe3)2]3 : Das erste Beispiel eines stabilen Phosphanidovanadium(V)-Komplexes / tBuN=V[P(SiMe3)2]3: The First Example of a Stable Phosphanidovanadium(V) Complex
Authors: Preuss Fritz , Tabellion Frank
Published: February 2015

The synthesis of the first stable phosphanidovanadium(V) complex tBuN=V[P(SiMe3)2]3 is described. The compound has been investigated by 1H, 13C ,31P, 51V NMR spectroscopy. The results indicate an eighteen-electron complex.
Polysulfonylamine, CXXVII [1] Wasserstoffbrücken in kristallinen Onium-dimesylamiden: Ein robustes Achtring-Synthon als Bestandteil dreidimensionaler Wasserstoffbrückenmuster / Polysulfonylamines, CXXVII [1] Hydrogen Bonding in Crystalline Onium Dimesylamides: A Robust Eight-Membered Ring Synthon as a Component in Three-Dimensional Hydrogen Bonding Patterns
Authors: Wijaya Karna , Moers Oliver , Henschel Dagmar , Blaschette Armand , Jones Peter G.
Published: February 2015

In order to study crystal packings and hydrogen bonding frameworks, low-temperature X-ray structures were determined for three onium salts of general formula B H+(MeSO2)2N−, where BH+ is acetamidinium (1, monoclinic, space group P21/c, Z = 4), guanidinium (2, monoclinic, P21/c, Z = 4), or 4,6-diamino-2-thioxo-2,3-dihydropyrimidinium (3, monoclinic P21/n, Z = 4). In every case the ions create three-dimensional N − H ∙∙∙ N/O networks, in which all N − H donors of the cations and four (in 1) or five (2, 3) acceptors of the anion are involved; non-conventional secondary bonds, e.g. C − H ∙∙∙ O/N, do not play an important role in the packings. For the isotypic structures 1 and 2, congruencies and dissimilarities of the hydrogen bonding patterns are discussed in detail. Despite the structural and chemical differences between the cations and the way in which they are attached to the anion, each of the three structures displays a robust eight-membered ring synthon [N2 = R2
2(8), antidromic] constructed via two-centre hydrogen bonds from a syn, syn-sequence H − N − C (sp2) −N −H of the respective cation and a V-shaped O − S (sp3) − N fragment of the anion. Although the networks in 2 and 3 contain several N − H (∙∙∙ O)2 three-centre interactions, the two-point connectivity of the synthon is distinctly preserved. The results indicate that the (MeSO2)2N− ion may be utilized in crystal engineering as a dependable building block.
Polysulfonylamine, CXXVIII [1]. Disulfonylamido-Gold(I)-Komplexe mit Tetrahydrothiophen als Ligand / Polysulfonylamines, CXXVIII. Disulfonylamido-gold(I) Complexes with Tetrahydrothiophene as Ligand
Authors: Ahrens Birte , Jones Peter G.
Published: February 2015

The molecular gold(I) complexes di(methanesulfonyl)amido-/V-(tetrahydrothiophene)gold(I) (1), di(p-chlorobenzenesulfonyl)amido-/V-(tetrahydrothiophene)gold(I) (2), and di(p-iodobenzenesulfonyl) amido-/V-(tetrahydrothiophene)gold(I) (3), were synthesised from (tetrahydrothiophene) chlorogold(I) and the appropriate silver salt. Crystal structure analyses were performed for all three compounds (3 both solvent-free and as a dichloromethane solvate 3a) and revealed a variety of intermolecular contacts. Compound 1 crystallizes with four independent molecules, two of which are connected by a gold-gold interaction of 3.2869(8) Å; several short nonclassical hydrogen bonds of the form C-H · O (the shortest with H · O 2.31 A) are observed. In compound 2, cyclodimers are formed via Au · Au contacts of 3.3302(8) Å; additionally Cl · Cl contacts of 3.457(3) Å are observed. Both forms of compound 3 are characterized by Au · I contacts, somewhat longer in 3 (3.6 - 4.3 Å) than in 3a (3.4 - 3.5 Å). The di(arenesulfonyl)amide ligands in 2, 3 and 3a display approximate C2 symmetry
1,1′-Di(tert-butyl)metallocenium Cations. The X-Ray Crystal Structures of [M(C5H4
tBu)2]PF6 (M = Fe, Co) and [Co (C5H4
t Bu)2]2CoCl4
Authors: Herberhold Max , Cheng Yan-Xiang , Jin Guo-Xin , Milius Wolfgang
Published: February 2015

The hexafluorophosphate salts [Fe(C5H4
tBu)2]PF6 (1) and [Co(C5 H4
tBu)2]PF6 (2) crystallize in isotypic structures with centrosymmetric cations which have a staggered (transoid) conformation of the exactly parallel ring ligands (conformational angle τ = 180°). The tetrachlorocobaltate salt, [Co(C5H4
tBu)2 ]2 CoCl4 (3), contains one almost eclipsed (τ = 140.4°) and one almost staggered (τ = 101.4°) cobaltocenium cation; in both cases, the cyclopentadienyl ring planes are slightly inclined (by α = 5.4° and 4.1°, respectively) to give more room to the tert-butyl substituents which are bent away from the metal in all three complexes 1 - 3
peri-Interactions in Naphthalenes, 4 [1]. Hypercoordination in 8-Dimethylamino-naphth-1-yl Phosphorus Compounds
Authors: Schiemenz Günter Paulus , Pörksen Simon , Näther Christian
Published: February 2015

In an 8-dimethylamino-naphth-1-yl-phosphorane a dative N→P bond forms in spite of the spacer properties of the naphthalene skeleton. Its “normal” length, 213.2 pm, much too short to fill the perispace, forces the C10 skeleton into severe distortion. In the light of these properties peri distances d(N-P/Si) ≫250 pm in 8-dimethylamino-naphth-1-yl-phosphines, -silanes etc. are recognized as evidence for steric hindrance
Lewis-Säure/Base Addukte von TiCl4 und Methylpyridinen / Lewis Acid/Base Adducts of TiCl4 and Methylpyridines
Authors: Hensen Karl , Lemke Alexander , Bolte Michael
Published: February 2015

By the reaction of 2-methyl- and 2,6-dimethylpyridine the first neutral TiCl4L complexes (L = single bonded ligand) could be synthesized. The structures have been determined by single crystal X-ray methods. The best description of the molecular structure is a distorted trigonal bipyramid with the nitrogen base occupying an equatorial position. With 2,4-dimethylpyridine, a 1:2 adduct is formed, where the nitrogen bases are in trans-positions of a TiCl4N2-octahedron, as also confirmed by an X-ray analysis
Gold Clustering at Dimethylsulfoximine Me2S(O)NH
Authors: Hamel Armin , Hollatz Christian , Schier Annette , Schmidbaur Hubert
Published: February 2015

Gold Clustering, Dimethylsulfoximine Polyaurated complexes of the dimethylsulfoximide anion [Me2S(O)N]- have been prepared by reacting N-trimethylsilyl-dimethylsulfoximide with [(Ph3P)Au]BF4 in various molar ratios. With one or two equivalents of the gold(I) reagent only the dinuclear complex is obtained in high yield: {[(Ph3P)Au]2NS(O)Me2}+ BF4
- . With three or four equivalents only the trinuclear complex is produced: {[(Ph3P)Au]3NS(O)Me2}2+ 2 BF4
- . No mono- or tetra-auration was observed, respectively. The composition of the compounds has been confirmed by analytical and spectroscopic data, and the crystal structure of the dinuclear compound has been determined by single crystal X-ray diffraction of the dichloromethane solvate. The two gold atoms are found to be coordinated to the nitrogen atom with a small Au-N-Au angle of only 92.3(3)° and a short Au-Au distance of 2.9900(5) Å. The nitrogen atom is in a distorted trigonal pyramidal configuration which allows an intramolecular SO-Au contact. For the trinuclear complex a structure with a tetracoordinate nitrogen atom [SNAU3] is proposed which is analogous to the corresponding complexes of phosphinimines R3P=NH. With the ditertiary phosphine Ph2PCH2Ch2PPh2 (dppe) a cyclic dinuclear complex (dppe)Au2[NS(0 )Me2]BF4 can be synthesized starting from (dppe)Au2Cl2. The reaction of the phosphine-rich precursor [(Ph3P)2Au]BF4 with Me3SiNS(0 )Me2 in the molar ratio 2:1 affords a binuclear complex {[(Ph3P)2Au]2NS(0 )Me2}BF4 of an as yet unknown structure
Synthese und Kristallstrukturbestimmung von Silicium-Komplexen der Koordinationszahl sechs mit Dimethylpyridinen/ Syntheses and Crystal Structure Determination of Hexacoordinated Silicon-Complexes with Dimethylpyridines
Authors: Hensena Karl , Kettner Markus , Stumpf Thorsten , Bolte Michael
Published: February 2015

Trichlorosilane, HSiCl3, forms with 3,4-dimethylpyridine in aprotic solvents a crystalline l:2-compound which is stable at room temperature and readily soluble in CHCl3. Colourless crystals of the dicationic complex, [H2Si(3,4-dimethylpyridine)4]2+ 2Cl- · 6 CHCl3 (verified by X-ray structure analysis) are obtained by dismutation of HSiCl3(3,4-dimethylpyridine)2 in CHCl3 within one week at room temperature.29Si NM R indicates that SiCl4 is generated as a second product. H2SiCl2 with 2,4-dimethylpyridine as well as MeHSiBr2 with 3,5-dimethylpyridine in aprotic solvents form 1:2-compounds stable at room temperature. X-ray structure analyses in both cases establish neutral-complexes with a hexa-coordinated silicon atom
Reaktionen der Lithiumhydridosilylamide Me2(H)Si-N(Li)R (R = CMe3, SiMe3) mit Chlortrimethylstannan und Chlormethylsilanen Me4–nSiCln (n = 1-3)/ Reactions of Lithium Hydridosilylamides Me2(H)Si-N(Li)R (R = CMe3, SiMe3) with Chlorotrimethylstannane and Chloromethylsilanes Me4-nSiCln (n = 1 - 3)
Authors: Schneider Jan , Popowski Eckhard , Peulecke Normen
Published: February 2015

The under reflux conditions in n-octane stable lithium hydridosilylamides Me2(H)Si-N(Li)R (1: R = CMe3, 2: SiMe3) were allowed to react with chlorotrimethylstannane and chloromethylsilanes Me4-nSiCln (n = 1 - 3) in different molar ratios.

1 reacts with Me3SnCl in n-pentane to give the cyclodisilazane [Me2Si-NCMe3]2 (3) and Me3SnH. The reaction of 2 with Me3SnCl under the same conditions leads to a mixture of Me2 (H)Si-N(SnMe3)SiMe3 (5), [Me2Si-NSiMe3]2 (4), and to Me3SnH. In the reactions of 1 and 2 with chlorotrimethylstannane in tetrahydrofuran the corresponding N-stannylation products Me2(H)Si-N(SnMe3)R 5, 6 and very small amounts of (Me3Sn)2 are formed.

The results of the reactions of 1 and 2 with Me2SiCl2 and of 1 with MeSiCl3 in n-hexane show that hydrogen-chlorine-exchange proceeds between the reactants. With Me2SiCl2 the corresponding cyclodisilazanes [Me2Si-NR]2 3, 4, N-silylation products Me2(H)Si-N(SiMe2Cl)R 7b, 8b, and Me2(H)Si-N(SiMe2H)R 7c, 8c, and the silanes Me2SiHCl and Me2SiH2 are formed, the cyclodisilazanes being the main products. 1 and MeSiCl3 produce 3, Me2(H)Si-N(R′)CMe3 (7d: R′ = SiMeCl2, 7e: R' = SiMeCIH, 7f: R′ = SiM eH2) and MeSiH3. In comparison with the reaction of 1 with Me2SiCl2 the yield of cyclodisilazane is smaller and that of N-silylated compounds is higher. The reaction behaviour of 1 towards Me2SiCl2 and MeSiCl3 in THF is comparable to that in n-hexane.

No silanimine intermediates are observed in the reactions of 1 or 2 with the chloromethylsilanes Me4-nSiCln (n = 1 - 3) in the molar ratios 1:5 and 1:10.
The Madelung Function of Elpasolites
Authors: Marx Veit , Hundhammer Bernd
Published: February 2015

Madelung Energy, Coulomb Interaction, Elpasolite For binary ionic compounds the Madelung energy can be calculated using the Madelung constant, the ionic charges and the next neighbour distance of the ions only. For ternary and higher systems the well-known standard formula cannot be applied, because the ionic charges and distances combine in different ways. In the present work we calculate the Madelung energy of the quaternary elpasolite structure by straightforward computer summation and propose a Madelung function which describes the Madelung energy in dependence on the lattice constant and the free structural parameter. This function has been applied to several chemical compounds of the elpasolite type to determine the individual Madelung energy.
Diorgano(trichlorsiIyl)phosphane/ Diorgano(trichlorosilyl)phosphines
Authors: Wolfsberger W.
Published: February 2015

Some diorgano(trichlorosilyl)phosphines of the general formula R(C6H5)PSiCl3 (R = CH3 1a, C2H5 2a, C3H7 3a, and C5H11 4a) have been prepared by transsilylation reactions of the corresponding diorgano(trimethylsilyl)phosphines with silicium tetrachloride and characterized by elemental analyses and NMR spectra
Preparation and Crystal Structure of a Mixed Metal Assembly [Ni(phen)3][Cu(H-1pap)]2(NO3) · 8 H2O Featuring Octahedral Cationic and Square-planar Anionic Modules
Authors: Fritsky Igor O. , Świątek-Kozlowska Jolanta , Kapshuk Anatoliy A. , Kozłowski Henryk , Sliva Tatiana Yu. , Gumienna-Kontecka Elzbieta , Prisyazhnaya Elena V. , Iskenderov Turganbay S.
Published: February 2015

The new mixed metal assembly [Ni(phen)3][Cu(H-1pap)]2(NO3 ) · 8 H2O (2) (H2pap = CH3- C(=NO H)-C(O )-NH-(CH2)3-NH-C(O )-C(=NOH)-CH3) was obtained by co-crystallisation of [Li(H2O)4][Cu(H-1pap)] · 2 H2O (1) and tris(1,10-phenanthroline)nickel(II) nitrate and studied by means of X-ray crystallography (triclinic, space group P1, a = 13.471(3), b = 13.641(3), c = 15.401(3) Å, α = 108.21(3), β = 97.73(3), γ = 107.74(3)°, V = 2476.6(9) Å , Z = 2 ,R1 = 0.0677 for 4672 unique reflections with I > 2σ(I)). The assembly indicates a network structure and consists of isolated cationic and anionic modules (octahedral [Ni(phen)3]2+ and square-planar [Cu(H-1pap)]-), non-coordinated nitrate anions and solvating water molecules. The elements of the crystal structure are linked by interactions of different types: by an extended system of H bonds, stacking interactions between aromatic rings, long apical Cu-N contacts and specific π-π interaction between a deprotonated oxime group of the complex anion and a phenanthroline ligand
Long Chain Cinnamoic Acid Esters from Daphne Oleoides
Authors: Ullah Nisar , Qureshi S. A. , Anwar Saeed , Malik Abdul , Haslinger Ernst
Published: February 2015

Two new natural products, tridecyl and undecyl 3,4-dihydroxycinnamate, were isolated from the chloroform soluble fraction of the whole plant of Daphne oleoides. Their structures were established on the basis of modern spectroscopic techniques including 2D NMR
Tris[(triphenylphosphine)gold(I)]oxonium Dihydrogentrifluoride as the Product of an Attempted Preparation of [(Triphenylphosphine)gold(I)] Fluoride
Authors: Mathieson Trevor , Schier Annette , Schmidbaur Hubert
Published: February 2015

The reaction of equivalent quantities of (triphenylphosphine)gold chloride and silver fluoride in CH2Cl2/MeOH gives tris[(triphenylphosphine)gold(I)]oxonium dihydrogentrifluoride in good yield. This product is formed through the action of water in the reaction medium. Crystals of {[(Ph3P)Au)3O}- [H2F3]- 1.5 CH2CI2 (monoclinic, space group P21/c, Z = 4) contain the cations as hexanuclear dimers with short intra- and intermolecular Au-Au contacts. The structural details are similar to those of related salts with different anions. The [H2F3P anion is V-shaped with one symmetrical and one unsymmetrical F-H-F hydrogen bond and is best described as an addition compound of an HF molecule and a [F-H-F]- anion. The results indicate a high affinity of H2O/OH- for (phosphine)gold fluorides and - by the same token - prove that tri(gold)oxonium cations are stable to anhydrous HF and F- anions. By contrast, hydrochloric acid is known to degrade {[(R3P)Au]3O}+ affording (R3P)AuCl and water.
CD-Spectroscopic Investigations for the Determination of the Absolute Configuration of α-Alkylated 1,4-CycIohexanedione Derivatives
Authors: Fleischhauer Jörg , Gabriel Sven , Ender Dieter , Nühring Anja , Wollmer Axel
Published: February 2015

The absolute configuration of the conformationally flexible six membered ring system 2-methyl- and 2,6-dimethyl-l,4-cyclohexanedione monoethylene acetal was determined by comparison of measured and calculated CD spectra. The rotational strengths were calculated by means of the CNDO/S-method assuming R at the stereogenic center. The results were compared with the predictions made by the octant rule. The enantiomerically pure material was synthesized via the corresponding SAMP- and RAMP-hydrazones.
Darstellung, 11B-, 13C-NMR- und Schwingungsspektren von Cs2[B6H5(p-C6H4(NO2))] und Cs2[B6H5(C6H3-l-(CH3)-5-(NO2))] sowie Kristallstruktur von (CH2Py2)[B6Cl5(p-C6H4(NO2))]·CH3CN / Preparation, 11B , 13C-NMR and Vibrational Spectra of Cs2[B6H5(p-C6H4(NO2))], Cs2[B6H5 (C6H3-1 -(CH3 )-5-(NO2))] and Crystal Structure of (CH2Py2)[B6Cl5(p-C6H4(NO2))]·CH3CN
Authors: Zander S. , Preetz W.
Published: February 2015

The first aryl derivatives of c/oso-hexahydrohexaborate are formed by reaction of [B6H6]2- with 1-bromo-4-nitrobenzene and 2-bromo-5-nitrotoluene in acetonitrile at 80 °C. Cs2[B6H5- (1,4-C6H4(NO2))] and Cs2[B6H5(C6H3-1-(CH3)-5-(NO2))] can be isolated by ion exchange chromatography on diethylaminoethyl (DEAE) cellulose. Further treatment with /V-chlorosuccinimide yields the perhalogenated derivative (CH2Py2)[B6Cl5(1,4-Ph(NO2))]CH3CN which has been characterized by X-ray diffraction analysis (orthorhombic, space group P2( 2,2t, a = 9.810(4), b - 14.412(3), c - 18.586(9) A, Z = 4). The 11B NMR spectra of all compounds are consistent with a monosubstituted B6-cluster. The IR and Raman spectra exhibit characteristic BB, BH, CH, CC and NO vibrations, respectively.
3.4-D ihydro-1, 2, 3, 4-tetramethyl- pentafulvalene and its Conversion to Ferrocenes
Authors: Hilbig Harald , Köhler Frank H.
Published: February 2015

Reaction of tetramethylcyclopentenone and cyclopentadienyl anion gave the title pentafulvalene derivative. Its deprotonation with sodium or potassium hydride proceeded selectively at one of the methyl groups. The resulting 3,4-dihydro-1,3,4-trimethyl(2-methylene)pentafulvalenide ion was converted to the corresponding ferrocene which was obtained as two diasteroisomers in the ratio of 1/1.
Atomvolumen und Packungsdichte der Atome in metallischen Elementen Atomic Volume and Packing Density of Atoms in Metallic Elements
Authors: Hübner Sven , Trömel Martin
Published: February 2015

In the body-centered cubic structure and in closest sphere-packings the atoms are arranged to give structures with equal densities. A measure of the packing density of atoms is derived. Several crystal structures of elements, including the bcc structure and the closest sphere packings, represent a state of maximum density in which the atomic volume is characteristic of each element. From any crystal structure of an element its atomic volume in this state can be calculated to a good approximation.
Reactivity of Cobalt(III) Amine-Thiolate Complexes with Terminal and Bridging Thiolate Functions towards Hydrogen Peroxide
Authors: Kersting Berthold , Siedle Gabriel
Published: February 2015

The reactivity of CoIII amine-thiolate complexes with terminal and bridging thiolate functions towards oxidizing agents has been investigated. The mononuclear CoIII N3S3 complex [CoIII(L1)] (2) (H3L1 represents the hexadentate ligand N,N′,N″-Tris(2-thio-benzyl)-1,1,1 -tris- (aminomethyl)ethane) featuring three terminal thiolate ligands, and the binuclear N3CoIII- (μ-S)3CoIIIN3 complex [CoIII
2(L2)]3+ (4) (H3L2 = N,N′,N″-Tris-[2-thio-3-aminomethyl-5-terrbutyl- benzyl]-1,1,1-tris(aminomethyl)ethane) featuring three bridging thiolates were selected. Hydrogen peroxide was the oxidizing agent. Whereas the thiolato-bridged complex 4 is resistant towards oxidation by hydrogen peroxide, 2 undergoes a ligand-based oxidation reaction to give the amine-sulfinate complex [Co(L1′)] 5, where all three terminal thiolates have been oxidized to sulfinates without gross structural changes of the parent complex 2. In contrast to 4, the cyclic voltammogram of 2 reveals an irreversible oxidation wave at E = +0.52 V vs SCE which can be attributed to a ligand-centered oxidation reaction. 4 and 5 have been structurally characterized by X-ray crystallography.
Chemischer Transport intermetallischer Phasen III: Das System Co-Si / Chemical Vapour Transport of Intermetallic Phases III: The System Co -Si
Authors: Bosholm O. , Oppermann H. , Däbritz S.
Published: February 2015

Five phases exist in the system Co-Si: Co3Si, α- and β-Co2Si, CoSi and CoSi2. The phases α-Co2Si and CoSi could be prepared by chemical transport with iodine as transport agent in the temperature range between T1 (700 °C) and T2 (900 °C). In a attempted systematic clarification of the chemical transport reactions of all phases in the system, the effective transport equilibria were determined. Thermodynamic data show satisfactory agreement between calculation and experiment.
Complexation of Cobalt(II), Nickel(II), and Copper(II) Ions with Pyridine, 2-Methylpyridine, 3-Methylpyridine, and 4-Methylpyridine in Acetonitrile
Authors: Kurihara Makoto , Kawashima Takuji , Ozutsumi Kazuhiko
Published: February 2015

Thermodynamic data of the complexation of cobalt(II), nickel(II), and copper(II) ions with pyridine (py), 2-methylpyridine (2Me-py), 3-methylpyridine (3Me-py), and 4-methylpyridine (4Me-py) have been determined by calorimetry and spectrophotometry in acetonitrile (MeCN) containing 0.1 mol dm-3 (C2H5)4NClO4 as a constant ionic medium at 25 °C. The calorimetric and spectrophotometric data for py, 3Me-py, and 4Me-py revealed the formation of [ML]2+, [ML2]2+, [ML3]2+, and [ML4]2+ (M = Co2+, Ni2+, Cu2+; L = py, SMe-py, 4Me-py). For 2Me-py, on the other hand, the formation of only one complex, [M(2Me-py)]2+ (M = Co2+, Ni2+), was detected. The stepwise thermodynamic quantities and the individual electronic spectra of the complexes suggest that all of these have a six-coordinate octahedral structure. The stability of the [M(2Me-py)]2+ (M = Co2+, Ni2+) complexes is much lower than that of the corresponding py, 3Me-py, and 4Me-py complexes. The difference in the stability of the 2Me-py complexes is mainly due to their unfavorable entropy changes because the differences of enthalpies for all the complexes are not so significant. The free energies for the formation of the mono complexes follow the order Mn(II) > Co(II) > Ni(II) > Cu(II) < Zn(II) for the py, 3Me-py, and 4Me-py systems. The ΔH°1 values vary in the same order and the ΔS°1 values are similar. Hence, the stability difference of the mono complexes originates from the enthalpic term
An Expeditious Approach to Trisubstituted Chiral Tetrahydrofurans
Authors: Iqbal Fazila , Shekhani Mohammed Saleh , Malik Abdul , Parvez Masood , Riaz Uzma , Ali Zulfiqar , Khan Khalid Mohammed
Published: February 2015

Ozonolysis of 3,6-anhydro-4-0-(p-toluenesulphonyl)-D-glucal (9), obtained in four steps from D-glucose, provided the target compound 11. The structure and configurations of 9 and 11 have been determined by spectral studies and X-ray crystallography. Similar strategy with D-galactose provided the corresponding derivatives 10 and 12, respectively
Extraktionen von Ginsenosiden aus Ginseng-Wurzeln mit flüssigem Ammoniak, Methanol-Wasser oder Wasser/ Extractions of Ginsenosidesj from Ginseng Roots with Liquid Ammonia, Methanol-Water or Water
Authors: Cho In-Ho , Hohaus Eberhard , Lehnen Axel , Lentz Harro
Published: February 2015

Extractions of ginsenosides from ginseng roots with liquid ammonia, methanol/water (60:40; v/v) or water were carried out. The extracts have been analyzed qualitatively and quantitatively to valuate yield and selectivity of extractions of ginsenosides. Water supplied the lowest yield. The yields of extracts with liquid ammonia were higher than those with m ethanol-water (60%). Yields of the ginsenosides Rb1, Rb2, Rc and Rd by extracting with liquid ammonia are about twice as much as those of the extraction with methanol-water (60%). It was proved by HPLC that malonyl-ginsenosides m -Rb1 m-Rb2, m-Rc and m-Rd were converted to the corresponding neutral ginsenosides by extraction with liquid ammonia. Because of high yields of extracts and simultaneous increase of the contents of Rb1, Rb2, Rc and Rd the extraction with liquid ammonia is obviously superior to the other extraction methods.

Furtherm ore, ginsenosides from ginseng roots were extracted by alkaline methanol-water (60%) solutions. Alternatively, the extracts of the methanol-water (60%) extraction were treated with sodium hydroxide solution. Both methods convert also the malonyl-ginsenosides to neutral ginsenosides
Synthese und Kristallstruktur von 2,4-Bis(methyIamino)-2-pentenium - chlorid [1] / Synthesis and Crystal Structure of 2,4- Bis(methylamino)-2-pentenium Chloride [1]
Authors: Kuhn Norbert , Fahl Joanna , Fuchs Stefan , Henkel Gerald
Published: February 2015

The vinamidinium chloride C7H15N2Cl (5) is obtained from the corresponding vinamidine C7H14N2 (4) and HCl; the X-ray structure reveals a polymeric nature consisting of w-shaped cations connected with the chloride ions by hydrogen bonds
Synthesis, Characterization and Reactivity of a Diorganotin Thiocarboxylate: Dimethyl(thioacetato)-tin(IV) Chloride and its Reactions with Nucleophiles Exhibiting Desulfurization
Authors: Singh Neetu , Bhattacharya Subrato , Nöth Heinrich , Mayer Peter
Published: February 2015

Dimethyl(thioacetato)tin chloride (1) was synthesized by the reaction of dimethyltin dichloride with thioacetic acid in the presence of triethylamine. Compound 1 was subjected to hydrolysis under different reaction conditions in order to obtain sulfido/hydrosulfidotin compounds. Except for one case where the product was hexamethyl-1,3,5-trithia-2,4,6-tristannacyclohexane, (Me2SnS)3 (4), all other reactions led to desulfurization, and the products obtained were organostannoxane compounds, dinuclear tetramethyl-oxo-dichloroditin, {Me2SnCl2.Me2SnO}
2 (2), and tetraacetatodioxotetra( dimethyltin), (Me2Sn)4O2(O2CMe)4 (3). These complexes have been characterized by 1H, 13C, 119Sn NMR and FTIR spectroscopy, and compounds 2 - 4 also by X-ray crystallography. Density functional calculations were performed to explain the structure and reactivity of the compounds.
Hydrocarbon-bridged Metal Complexes, LII [1]. N1,N2-Di(tert-butoxycarbonyl)-1,2,4-triaminobutane, a Useful Reagent for the Synthesis of Hydrocarbon-bridged Bis(ethylenediamine) Ligands by Reactions with Dicarboxylic Acids
Authors: Miller Bernhard , Altman Janina , Beck Wolfgang
Published: February 2015

The reactions of N1,N2-Di-boc-1,2,4-triaminobutane with bridged dicarboxylic acids afford the corresponding bis-amides from which - after removal of the Boc groups - bis(N,N'-bidendate) ligands H2NCH2CH(NH2)(CH2)2NHCO-X-CONH(CH2)2CH(NH2)CH2NH2 can be obtained. New examples are the reactions of the triaminobutane with pyridine-2,6-dicarboxylic acid, with phenylene- 1,4-diacetic acid, with terephthalic acid dichloride and with benzene-1,2,4,5-tetracarboxylic acid. From the new ligands with two terminal ethylenediamine groups, the bis(dichloroplatinum) complexes were synthesized
Metal Complexes of Biologically Important Ligands, CLXXI [1]. Incorporation of the cis-Dichloroplatinum Group into Amides of 3,4-Diarylpyrrole-2,5-dicarboxylic Acids
Authors: Miller Bernhard , Terpin Andreas , Steglich Wolfgang , Beck Wolfgang
Published: February 2015

3,4-Bisarylpyrrole-2,5-dicarboxylic acids were coupled with rac-N1,N2-di-Boc-1,2,4-triaminobutane to give the corresponding diamides, which were deprotected and converted into the bis(cis-dichloroplatinum) complexes by treatment with K2PtCl4
Hydrocarbon-bridged Metal Complexes, LIII [1]. Trinuclear (cis-Dichloro-ethylenediamine) Platinum(II) Complexes from Amides of Tricarboxylic Acids and 1,2,4-Triaminobutane
Authors: Miller Bernhard , Beck Wolfgang
Published: February 2015

The coupling of the tricarboxylic acids, 1,3,5-benzene-tricarboxylic acid, cis,cis-1,3,5-cyclohexane- tricarboxylic acid and of citric acid, with rac-N1,N2-di-Boc-1,2,4-triaminobutane affords the corresponding triamides which were deprotected. From the novel tris(bidendate) ligands with three terminal ethylenediamine donors the tris(cis-dichloro platinum) complexes were obtained
Rare Earth-rich Cadmium Compounds RE23T7Cd4 (T = Co, Ni, Ru, Rh, Ir, Pt)
Authors: Tappe Frank , Pöttgen Rainer
Published: February 2015

The rare earth-rich intermetallic compounds RE23T7CD4(RE = La-Nd, Sm, Gd, Tb; T = Co, Ni, Ru, Rh, Ir, Pt) were synthesized by melting of the elements in sealed tantalum tubes in a high frequency furnace. They crystallize with the Pr23Ir7Mg4-type structure, space group P63mc, Z = 2. The structures of La23Pt7Cd4 (a = 1025.4(2), c = 2319.5(5) pm, wR2 = 0.0425, 2587 F2, 74 variables), La23Ru6.87(1)Cd4 (a = 1015.0(2), c = 2282.8(4) pm, wR2 = 0.0383, 2459 F2, 75 variables), and Nd23Rh7Cd4 (a = 990.0(2), c = 2239.0(5) pm, wR2 = 0.0507, 2350 F2, 74 variables) were refined from single crystal X-ray diffractometer data. Central structural motifs of the RE23 T7Cd4 compounds are transition metal-centered trigonal prisms of rare earth atoms and Cd4 tetrahedra. The RE6T prisms are condensed via common edges and corners, leading to three-dimensional networks. Typical interatomic distances in the prismatic network and in the Cd4 tetrahedra are 295 - 313 pm La-Pt and 319 - 325 pm Cd-Cd, respectively (examplarily for La23Pt7Cd4)
Lanthanoiddisulfide – Synthesen und Kristallstrukturen von α-CeS2, α-NdS2, β-LaS2, β-CeS2 und β-PrS2 / Rare Earth Metal Disulfides – Syntheses and Crystal Structures of α-CeS2, α-NdS2, β -LaS2, β -CeS2, and β -PrS2
Authors: Schleid Thomas , Lauxmann Petra , Bartschb Christian , Doert Thomas
Published: February 2015

α-CeS2 and α-NdS2 were obtained by a metathesis reaction of the anhydrous trichlorides LnCl3 (Ln = Ce, Nd) and Na2S2 at 1070 K. The two compounds adopt a monoclinic structure type, the so-called CeSe2 or α-type of the rare earth metal dichalcogenides (space group P21/a), with lattice parameters of a = 8.105(3), b = 4.075(1), c = 8.097(3) Å, β = 90.03(4)◦ for CeS2 and a = 8.008(2), b = 4.019(1), c = 8.032(2) Å , β = 90.00(3)◦ for NdS2. Single crystals of β -LaS2, β -CeS2 and β -PrS2 were obtained as by-products in the syntheses of the ternary copper sulfides CuLnS2 by reacting the elemental educts (Cu, S and Ln = La, Ce, Pr) in a CsCl flux at 970 K. These compounds adopt the orthorhombic β -LaS2 structure type (space group Pnma) with lattice parameters of a = 8.140(1), b = 16.379(1), c = 4.144(1) Å for β -LaS2, a = 8.068(1), b = 16.216(1), c = 4.095(1) Å for β -CeS2, and a = 8.044(1), b = 16.160(1), c = 4.073(1) Å for β -PrS2
Syntheses and Structures of Trinuclear Trigonal-bipyramidal Silver(I) Complexes with Bis(diphenylphosphino)amide Ligands
Authors: Shi Hua-Tian , Duan Taike , Xu Chao , Zhang Qian-Feng
Published: February 2015

Treatment of Ag(CF3CO2) with an equivalent of bis(diphenylphosphino)amide (dppa) gave a trinuclear trigonal-bipyramidal silver(I) complex [Ag3(μ3-Cl)2(μ-dppa)3][CF3CO2]・CH2Cl2・H2O ([1] [CF3CO2]・CH2Cl2・H2O). Reaction of AgNO3 with an equivalent of dppa in the presence of [NH4] [GaCl4] and [Et4N][FeCl4] afforded the corresponding complexes [Ag3(μ3-Cl)2(μ-dppa)3][GaCl4]・ 2THF・MeOH・H2O, ([1][GaCl4]・2THF・MeOH・H2O) and [Ag3(μ-Cl)(μ3-Cl)(μ-dppa)3][FeCl4], ([2] [FeCl4]), respectively. Complexes 1 and 2 contain trigonal-bipyramidal [Ag3(μ3-Cl)2]+ and [Ag3(μ- Cl)(μ3-Cl)]+ cores, respectively, surrounded by three bridging μ-dppa ligands
Structural Transformation from Trinuclear Linear to Tetranuclear Cubane Heterobimetallic Selenium Compounds. Structure and Optical Linearities of [Et4N]2[(μ-WSe4)(CuCl)2]
Authors: Liu Shu-Lei , Duan Taike , Zhang Qian-Feng , Leung Wa-Hung
Published: February 2015

Reactions of [Et4N]2[WSe4] with two equivalents of [CuX] powder gave trinuclear linear compounds [Et4N]2[(μ-WSe4)(CuX)2] (X = Cl 1, Br 2). Treatment of 1 or 2 with PPh3 in CH2Cl2 resulted in the formation of tetranuclear cubane-like compounds (μ3-X)(μ3-WSe4)(CuPPh3)3 (X = Cl 3, Br 4). The structures of the heterobimetallic selenium compounds 1 and 4・MeCN were confirmed by single-crystal X-ray diffraction. The nonlinear optical properties of 1 were investigated at λ = 532 nm with a pulse width of 7 ns
A New Blue-emitting Diimine Copper(I) Complex: Synthesis, Crystal Structure and Photophysical Properties
Authors: Ying Jun , Tian Ai-xiang , Li Bin
Published: February 2015

A new diimine Cu(I) complex, [Cu(DPEphos)(DPOP)]BF4 ・CH2Cl2 (1) (DPEphos = bis[2- (diphenylphosphino)phenyl]-ether, DPOP = 2-(11-dipyrido[3,2-a:2ʹ,3ʹ-c]phenazine)-5-p-tolyl-1,3,4- oxadiazole), has been synthesized and characterized by X-ray single-crystal diffraction analysis. In crystals of complex 1, the [Cu(DPEphos)(DPOP)]+ cations are arranged in supramolecular chains, just like a “zipper”. Cation layers and anion layers are alternating in this structure. The photophysical behavior of DPOP and 1 was studied.
Efficient One-pot Synthesis of 4-Ethynylbenzenesulfonamides
Authors: Zhang Wensheng , Kuang Chunxiang , Yang Qing
Published: February 2015

One-pot simultaneous debrominative decarboxylation and sulfamation of anti-2,3-dibromo-3-(4- chlorosulfonylphenyl)propanoic acid in DMF (for alkylamines) or DMF-pyridine (1/1, for arylamines) using a diverse range of alkyl and aryl amines under microwave irradiation stereoselectively afforded intermediate (Z)-4-(2-bromovinyl)benzenesulfonamides. The intermediates, without isolation and purification, were treated with EtONa to give the desired 4-ethynylbenzenesulfonamides.
A Coordination Polymer of Bis-[2-(dimethylamino)ethanolato]dimethylsilane with a Lithium Chloride Dimer
Authors: Hagemann Michael , Pape Tania , Mitzel Norbert W.
Published: February 2015

The reaction of lithium 2-(dimethylamino)ethanolate with Me2SiCl2 yielded a lithium chloride adduct of Me2Si- (OCH2CH2NMe2)2. Despite the application of an excess of Me2SiCl2, the formation of ClMe2SiOCH2CH2NMe2 was not observed. [Me2Si(OCH2CH2NMe2)2・Li2Cl2] was characterised by NMR spectroscopy and determination of its crystal structure by X-ray diffraction. In the solid state it forms endless chains consisting of Li2Cl2 rhombi, with the lithium atoms chelated by the O and N atom of one OCH2- CH2NMe2 substituent of Me2Si(OCH2CH2NMe2)2 units.
Drastic Decrease of the Curie Temperature in the Solid Solution GdRuxCd1–x
Authors: Tappe Frank , Schappacher Falko M. , Hermes Wilfried , Eul Matthias , Pöttgen Rainer
Published: February 2015

Five samples of solid solutions GdRuxCd1−x extending up to x ≈ 0.25 were synthesized by induction-melting of the elements in sealed tantalum tubes. According to X-ray powder diffraction data, the GdRuxCd1−x samples crystallize with the cubic CsCl structure. The structures of two crystals were refined from diffractometer data: Pm3̄m, a = 372.41(4) pm, wR2 = 0.0363, 45 F2, 5 variables for GdRu0.10(1)Cd0.90(1) and a = 367.70(4) pm, wR2 = 0.0301, 39 F2, 5 variables for GdRu0.20(1)Cd0.80(1). The cadmium-ruthenium substitution has a drastic effect on the magnetic properties. All samples order ferromagnetically, however, the Curie temperature decreases drastically from 258 K for GdCd to 63.6 K for GdRu0.20Cd0.80 with a Vegard-type behavior.
Die Selten-Erd-Metall(III)-Fluorid-Oxoselenate(IV) MF[SeO3] (M = Y, Ho–Lu) imYF[SeO3]-Typ/ The Rare-Earth Metal(III) Fluoride Oxoselenates(IV) MF[SeO3] (M = Y, Ho–Lu) with YF[SeO3]-type Structure
Authors: Lipp Christian , Schleid Thomas
Published: February 2015

YF[SeO3]-type rare-earth metal(III) fluoride oxoselenates(IV) MF[SeO3] (M = Y, Ho-Lu) crystallize monoclinically in space group P21/c (no. 14) with Z = 4. Obeying the lanthanoid contraction, the lattice parameters decrease successively from a = 657.65(7), b = 689.71(7), c = 717.28(7) pm and β = 99.036(5)° for YF[SeO3] at 298 K to a = 648.39(6), b = 681.28(7), c = 705.81(7) pm and β = 98.657(5)° for LuF[SeO3] at 100 K (LT-LuF[SeO3], LT ≡ Low Temperature). The M3+ cations are occupying the general site 4e. Contrary to the triclinic structure of RT-LuF[SeO3] (RT ≡ Room Temperature; CN(Lu3+) = 7) the higher coordination number eight is achieved for the M3+ cations in all YF[SeO3]-type compounds. This results in [MO6F2]11− polyhedra (d(M-O) = 228 - 243/225 - 239 plus 263/258 pm, d(M-F) = 219/216 pm, M = Y/Lu), which are connected via common O・ ・ ・O edges to form infinite chains 1
∞{[MOe
4/2Ot
2/1Ft
2/1]7−} (e ≡ edge-sharing, t ≡ terminal) running along [010]. Neighboring chains share common O3・ ・ ・O3 and O3・ ・ ・F edges generating 2
∞{[M(O3)3/3(O2)2/2(O1)1/1F2/2]4−} sheets parallel to the (100) plane. Finally, these 2
∞{[MO3F]4−} sheets are interconnected by Se4+ cations, which appear in isolated ψ1-tetrahedral [SeO3]2− anions (d(Se-O) = 167 - 175 pm). For the synthesis of the YF[SeO3]-type rare-earth metal(III) fluoride oxoselenates( IV) MF[SeO3] (M = Y, Ho-Lu), the rare-earth metal sesquioxides (M2O3) and trifluorides (MF3), and selenium dioxide (SeO2) in molar ratios of 1 : 1 : 3 with the fluxing agent CsBr were reacted within five days at 700 - 750 °C in evacuated graphitized silica ampoules.
Key words: Titanium(IV), Hydrazone, Schiff Base, Molecular Structure, Cyclic Voltammetry
Authors: Afsah Elsayed M. , Fadda Ahmed A. , Bondock Samir , Hammouda Mohamed M.
Published: February 2015

Tetrahydro-1H-benzo[b]azonin-2,7-dione (2a) has been used as a precursor in the synthesis of dibenzo[ b,f ][1,5]diazacyclododecene and dibenzo[b,g][1,6]diazacyclododecene ring systems 4 and 5, respectively, via periodate oxidation of the appropriate indolo-benzo[b]azonines 3 and 7. The synthesis of hexahydro-benzo[b][1,4]diazecin-2,7-dione (10) has been achieved by the Schmidt reaction of 2a.

The periodate oxidation of 9,9´-methylenebis(2,3,4,9-tetrahydro-1H-carbazole) (11) afforded 1,1´- methylenebis(3,4,5,6-tetrahydro-1H-benzo[b]azonin-2,7-dione) (12). Its 6,6´-methylenebis isomer 13 was obtained by treating 2a with formaldehyde. Oxidation of 16 gave the unsymmetrical bi(benzo [b]azonine) 17.

The Mannich reaction of 2a led to a mixture of its 6-methylene derivative 19 and the spirocyclic system 20. The reactions of 2a with aldimines and aromatic aldehydes were also investigated.
Synthesis of Some New Indolizine and Pyrrolo[1,2-a]quinoline Derivatives via Nitrogen Ylides
Authors: Dawood Kamal M. , Ragab Eman A. , Mohamed Sanaa N.
Published: February 2015

Pyridine and quinoline react with 3-bromoacetyl-1,5-diphenyl-1H-pyrazole-4-carbonitrile (2) in dry benzene to give the corresponding pyridinium and quinolinium salts 3 and 9. The latter salts undergo [3+2] 1,3-dipolar cycloaddition with some acetylene and ethylene derivatives to give the corresponding indolizine and pyrrolo[1,2-a]quinoline derivatives
Bioactive Phenylethanoids and Coumarines from Basalmocitrus cameroonensis
Authors: Wansi Jean Duplex , Djouaka Bavoua Judith Liliane , Ngeufa Happi Emmanuel , Prasad Devkota Krishna , Ndjakou Lenta Bruno , Mesaik Muhammed Ahmed , Choudhary Muhammad Iqbal , Tanee Fomum Zacharias , Sewald Norbert
Published: February 2015

Two new phenylethanoids, basalethanoid A (1) and B (2), and one new ceramide, basalamide A (3), together with eleven known compounds (4 - 14) were isolated from theMeOH extract of the stem barks of Basalmocitrus cameroonensis. The structures of all compounds were determined by comprehensive analyses of their 1D and 2D NMR, mass spectral (EI and ESI) data, chemical reactions, and comparison with previously known analogs. Compounds 1, 2, 5, and 7 - 10 demonstrated a strong inhibition on reactive oxygen species (ROS) production in the oxidative burst activity of whole blood on activation with serum opsonized zymosan in the range of IC50 = 0.06 - 12.30 μg mL−1.
The First Total Synthesis of Galloyl Tyramine
Authors: Ullah Nisar
Published: February 2015

The first total synthesis of galloyl tyramine, an inhibitor of Pim2 kinase was accomplished in an overall high-yield reaction sequence
Cadmium-Auride AIICdxAu2– x (AII = Ca, Sr) Synthese, Kristallstruktur, chemische Bindung/ Cadmium-Aurides AIICdxAu2−x (AII = Ca, Sr) – Synthesis, Crystal Structure, Chemical Bonding
Authors: Harms Wiebke , Dürr Ines , Röhr Caroline
Published: February 2015

Following the observation that the binary dicadmides and diaurides of calcium and strontium (A) both form the KHg2 structure type, the two sections AIICdxAu2−x have been studied systematically by means of synthetic, X-ray structural and theoretical investigations. The binary border compound CaCd2 is dimorphic forming the KHg2 structure at elevated temperatures (orthorhombic, space group Imma, a = 488.63(9), b = 754.1(2), c = 851.3(2) pm, Z = 4, R1 = 0.0498) and the MgZn2-type Laves phase at ambient conditions (hexagonal, space group P63/mmc, a = 599.71(9), c = 962.7(2) pm, Z = 4, R1 = 0.0309). Starting from the known binary calcium auride CaAu2 only a very small amount of Au can be replaced by Cd. Around the 1 : 1 ratio of Au and Cd the TiNiSi structure type (orthorhombic, space group Pnma), an ordered variant of the KHg2 type, has a small homogeneity range (CaCdxAu2−x with x = 1/0.76(2): a = 735.0(1)/731.7(1), b = 433.66(6)/431.43(7), c = 873.7(2)/869.9(2) pm, Z = 4, R1 = 0.0482/0.0539). The analogous structure type is also observed in the Sr compounds with the difference that in this case a continuous transition from the KHg2 type of SrAu2 (i. e. x = 0) towards the distorted TiNiSi structure type (up to x = 0.86) is observed in the series SrCdxAu2−x (for x = 0.86(1)/0.45(1): a = 764.0(1)/758.4(1), b = 458.07(7)/474.6(1), c = 872.16(12)/829.2(2) pm, Z = 4, R1 = 0.0446/0.0410). Attempts to prepare the Ca compounds of intermediate composition around a Cd content of x ≈ 0.5 resulted in the formation of the Aurich phase Ca5Cd2Au10 crystallizing with the Zr7Ni10 structure type (orthorhombic, space group Cmca, a = 1390.6(4), b = 1015.7(3), c = 1025.6(2) pm, Z = 4, R1 = 0.0657). In this compound, Cd and Ca occupy common crystallographic sites, which are occupied by In in the isotypic ternary compound Ca4In3Au10. Similarly, at the Cd-rich parts of the sections AIICdxAu2−x no simple phase width of the KHg2 structure type exists. In the case of the calcium series the new compound Ca11Cd18Au4, which shows only a very small phase width, is formed instead. This compound crystallizes with a new structure type (Ca11Cd18+xAu4−x with x = 0.6/0: tetragonal, space group I41/amd, a = 1030.83(6)/1029.39(6), c = 3062.5(3)/3051.0(3) pm, Z = 4, R1 = 0.0475/0.0379) exhibiting a complicated Cd/Au polyanion with four-, five- and six-bonded Cd/Au atoms. The results of FPLAPWband structure calculations are used to explain the electronic stability of the compounds. The calculated Bader charges of cadmium and gold atoms (and In and Au atoms for comparison) are used to discuss the transition between Cd-rich cadmides (like CaCd2 and Ca11Cd18Au4), auridocadmates (like CaCdAu) and the Cd-poor cadmium aurides (like Ca5Cd2Au10).