bluuebunny/crossref_metadata_2025 huggingface dataset:
1,2-Hydroboration of Alkyn-1-yl(chloro)silanes: Alkenes Bearing Chlorosilyl and Dialkylboryl Groups in Geminal Positions
Authors: Wrackmeyer Bernd , Khan Ezzat , Kempe Rhett
Published: February 2015

The 1,2-hydroboration of various alkyn-1-yl(chloro)silanes (3 - 7), derived from 1-hexyne (a) and ethynylbenzene (b), using 9-borabicyclo[3.3.1]nonane, 9-BBN, affords selectively alkene derivatives in which the dialkylboryl and chlorosilyl groups are in geminal positions at the C=C bond. The molecular structure of (Z)-α-(9-borabicyclo[3.3.1]non-9-yl)-α-dichloro(phenyl)silyl-styrene (11b) was determined by X-ray diffraction. All alkenes were characterised by a consistent set of NMR spectroscopic data (1H, 11B, 13C, 29Si NMR).
Acylation of Tropane Alkaloids Displaying Reversed Diastereoselectivities under Enzymatic versus Chemical Conditions
Authors: Affolter Olena , Baro Angelika , Laschat Sabine , Fischer Peter
Published: February 2015

Lipase-mediated monoacetylation of 6,7-dihydroxytropinones 4 gave acetates 5, ent-5 which were analyzed as Mosher esters 9a, b by 1H NMR spectroscopy. However, the hydroxy groups in 4 were not differentiated by lipases. Reduction of the keto function and subsequent silylation afforded a mixture of endo/exo-TBS ethers 11, which were dihydroxylated to give the corresponding diols endo/exo-12. In chemical acetylation a change of the endo/exo ratio in favor of the endo-derivative endo-13 was observed, whereas the formation of the exo-acetate exo-13 dominated in lipase-catalyzed acylation reactions. A mechanistic proposal is given.
Interionische C–H···O-Brückenbindungen in 1,3-Diisopropyl-4,5- dimethylimidazolium-2-nitrodiethylmalonat [1] / Interionic C–H· · ·O Hydrogen Bonds in 1,3-Diisopropyl-4,5-dimethylimidazolium-2- nitrodiethylmalonate [1]
Authors: Kuhn Norbert , Maichle-Mößmer Cäcilia , Steimann Manfred , Sweidan Kamal
Published: February 2015

1,3-Diisopropyl-4,5-dimethylimidazolium 2-nitrodiethylmalonate (2) was obtained from 2,3- dihydro-1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene (1) and 2-nitrodiethylmalonate; its crystal structure reveals the presence of interionic bifurcated C-H· · ·O hydrogen bonds.
Studies with 6,7-Dimethoxy-3,4-dihydroisoquinolin-1-yl-acetonitrile: Novel Syntheses of 1-Azolyl- and Pyridoisoquinolines
Authors: Hassaneen Huwaida M. E. , Awad Enas M. , Hassaneen Hamdi M.
Published: February 2015

The reaction of 3,4-dihydroisoquinolin-1-yl-acetonitrile with DMFDMA afforded the enaminonitrile 5. Compound 5 was reacted with 2-aminobenzimidazole to yield 4-amino-3-(dihydroisoquinolin- 1-yl)-benzo[4,5]imidazo[1,2-a]pyrimidine (11) and with acetonitrile derivatives to afford pyrido[2,1- a]isoquinolines (15a - g).
Sesquiterpenes and Phenolic Compounds from Achillea clypeolata Sesquiterpenes and Phenolic Compounds from Achillea clypeolata
Authors: Werner Ingrid , Mucaji Pavel , Presser Armin , Glasl Sabine
Published: February 2015

The investigation of a dichloromethane extract of flower heads of Achillea clypeolata collected in Bulgaria led to the isolation of one guaiane (4,10,11-trihydroxy-guaiane, 1), four eudesmanes (4(15)-eudesmene-1β ,11-diol, 2, clypeotriol, 3, 3-epi-clypeotriol, 4, cryptomeridiol, 5), one diterpene (sugeroside, 6) and two phenolic compounds (centaureidin, 7 and scopoletin, 8). Their structures were elucidated by UV/vis, EI- and CI-MS as well as by one- and two-dimensional NMR experiments. 4,10,11-Trihydroxy-guaiane (1) and 3-epi-clypeotriol (4) are reported here for the first time.
Sterols from a Vietnamese Wood-Rotting Phellinus sp.
Authors: Quang Dang Ngoc , Bach Dang Dinh , Asakawa Yoshinori
Published: February 2015

Phytochemical examination of the methanolic extract from fruit bodies of an unidentified Vietnamese Phellinus species led to the isolation of four compounds, one of which is a new steroid, 25-hydroxy-ergosta-7,24(28)-dien-3β -ol, named phellinol, together with senexonol, trametenolic acid B and ergosta-4,6,8(14),22-tetraen-3-one. Their structures were determined by 2D NMR, MS, IR and UV spectroscopy. In addition, the absolute configuration of senexonol was established by X-ray crystallographic analysis of its p-bromobenzoate derivative as 22(R)-hydroxy-4(S),14(S)- dimethyl-cholesta-8,24-dien-3-one. All compounds moderately suppressed the lipopolysaccharide (LPS)-induced production of nitric oxide (NO) in RAW 264.7 cells.
C–H Bond Activation ofMethane with Gaseous [(CH3)Pt(L)]+ Complexes (L = Pyridine, Bipyridine, and Phenanthroline)
Authors: Butschke Burkhard , Schlangen Maria , Schwarz Helmut , Schröder Detlef
Published: February 2015

Electrospray ionization of solutions of dimethyl(1,5-cyclooctadiene)platinum(II) in methanol with traces of nitrogen-containing ligands L provides gaseous complexes of the type [(CH3)Pt(L)]+ with L = pyridine (py), 2,2′-bipyridine (bipy), and 1,10-phenanthroline (phen). These [(CH3)Pt(L)]+ cations are capable of activating the C-H bond in methane as shown by H/D exchange when using CD4 as a neutral reactant. Most reactive is the complex [(CH3)Pt(py)]+ bearing a monodentate nitrogen ligand. The cationic complexes [(CH3)Pt(bipy)]+ and [(CH3)Pt(phen)]+ also bring about activation of methane, though at a lower rate, whereas the bipyridine complex [(CH3)Pt(py)2]+ does not react with methane at thermal conditions. A detailed analysis of the experimental data by means of kinetic modeling provides insight into the underlying mechanistic steps, but a distinction whether the reaction occurs as σ bond metathesis or via an oxidative addition cannot be made on the basis of the experimental data available.
Boryl-substituted Zirconocene Dichloride Complexes as Catalyst Precursors for Homogeneous Ethylene Polymerization
Authors: Kestel-Jakob Alexandra , Alt Helmut G.
Published: February 2015

The synthesis and characterization of 16 new boryl-substituted zirconocene dichloride complexes are reported. After activation with methyl aluminoxane (MAO) these complexes are catalysts for homogeneous ethylene polymerization. The combination of these complexes with nickel catalysts containing Lewis basic substituents produces polymers with bimodal molecular weight distributions.
Poly(pyrazol-1-ylmethyl)benzene Palladium Complexes: Synthesis, Characterisation and Evaluation as Heck Coupling Catalysts
Authors: Motsoane Nthabiseng M. , Guzei Ilia A. , Darkwa James
Published: February 2015

The poly(pyrazol-1-ylmethyl)benzenes L1 - L5 react with [PdCl2(NCMe)2] or [PdClMe(COD)] to form dinuclear palladium complexes [{PdClX(3,5-Me2pzCH2)2-1,2-C6H4}2] (X = Cl (1), Me (2)), [{PdCl2(3,5-Me2pzCH2)2-1,3-C6H4}2] (3), palladium complexes [{Pd2(μ-Cl)2Me2(3,5- Me2pzCH2)2-1,3-C6H4}] (4), [{Pd2(μ-Cl)2X2(3,5-Me2pzCH2)2-1,4-C6H4}] (X = Cl (5), Me (6)), [{Pd2(μ-Cl)2Cl2(3,5-tBu2pzCH2)2-1,4-C6H4}] (7), and tetranuclear [{Pd2(μ-Cl)2Cl2(3,5- Me2pzCH2)2}2-1,4-C6H4] (8). The structures of 1, 2 and 8 were confirmed by X-ray structure analysis. The complexes efficiently catalyse the coupling reaction of iodobenzene and butylacrylate at 80 °C.
Tri(3-pyridyl)phosphine as Amphiphilic Ligand in the Rhodium-catalysed Hydroformylation of 1-Hexene
Authors: Meyer Wolfgang H. , Bowen Richard J. , Billing David G.
Published: February 2015

The molecular structure of carbonylchlorobis(tri(3-pyridyl)phosphine)rhodium, 1, has been determined by X-ray diffraction methods. The N-protonated trifluoromethanesulfonate (triflate) complex 3 was synthesised as a model compound for the extraction of a rhodium complex bearing amphiphilic ligands which can allow catalyst recycling in the hydroformylation of alkenes by using their distribution behavior in organic and aqueous solvents of different pH. The high water-solubility of the employed ligand renders the recycling method as only partly successful due to insufficient extraction from the water phase into the organic phase. In the hydroformylation of 1-hexene the production of n-heptanal is slightly disfavoured when using the ligand tri(3-pyridyl)phosphine as compared to triphenylphosphine which can be ascribed to a higher amount of ligand-deficient active rhodium complexes of the less basic pyridyl phosphine ligand under CO pressure.
Molecular Structures and Catalytic Activity of Palladium Complexes Derived from Lutidine-bridged Bis(benzimidazolin-2-ylidene) Ligands
Authors: Jahnke Mareike C. , Pape Tania , Hahn F. Ekkehardt
Published: February 2015

Reaction of lutidine-bridged dibenzimidazolium dibromides 1 - 4 with palladium acetate gives pincer-type palladium complexes of the type [Pd(L)Br]Br [5]Br-[8]Br. Crystals suitable for an X-ray diffraction study have been obtained by slow evaporation of the solvent from dichloromethane/methanol solutions of [7]Br and [8]Br. The crystal structure of [7]+ reveals a pincer topology of the cationic complex with a distorted square-planar coordination geometry at the metal center. From a solution of complex [8]Br, a dinuclear byproduct [9]+ was obtained with two bis(benzimidazolin- 2-ylidene) ligands coordinating in a bridging fashion. The pincer-type palladium complexes [5]Br- [8]Br were tested as precatalysts in Suzuki coupling reactions.
The Affinity of Indium(III) for Nitrogen-donor Ligands in Aqueous Solution. A Study of the Complexing of Indium(III) with Polyamines by Differential Pulse Voltammetry, Density Functional Theory, and Crystallography
Authors: Harrington James M , Oscarson Karen A. , Jones S. Bart , Reibenspies Joseph H. , Bartolotti Libero J. , Hancock Robert D.
Published: February 2015

The affinity of In(III) for N-donor ligands was investigated by differential pulse voltammetry, DFT calculations, and crystallography. The structure of [In(tpen)(CH3COO)](ClO4)2 ・ 0.5H2O (1) is reported (tpen = N,N,N´ ,N´-tetrakis(2-pyridylmethyl)ethylenediamine): Monoclinic, P21/n, a = 8.687(4), b = 7.767(8), c = 20.432(10) Å , β = 93.372(8)°, Z = 4, R = 0.0518. The In(III) center is 7-coordinate, with six In-N bonds to the tpen ligand in the range 2.306 - 2.410 Å, and a unidentate acetate group with In-O = 2.247 Å. The formation constants of In3+ in 0.1 M NaNO3+ at 25 °C are (M = In(III), L = ligand, H = proton): L = triethylenetetramine, logβ (MLH2) = 25.3±}0.3, logK1 = 14.43±}0.09, and logβ (ML(OH)2) = 27.7±}0.1; tetraethylenepentamine, logβ (MLH) = 20.8±}0.2, and ML (logβ (ML) = 20.1±}0.3); diglycolic acid, (logβ (MLH) = 8.06±}0.06), logK1 = 6.02±} 0.06, logβ2 = 9.40±}0.08; tpen, logK1 = 17.71±}0.07; N,N´-bis(2-pyridylmethyl)ethylenediamine, logK1 = 14.69±}0.05; 1,10-phenanthroline, logK1 = 6.81±}0.07, logK2 = 6.44±}0.07, logK3 = 6.20±}0.08. Correlations are shown between the determined formation constants for the polyamines and logK1(NH3) values for a wide variety of metal ions. For M(II) ions, the log K1(NH3) values are experimental data, but for M(III) ions the data are predicted by an empirical dual-basicity equation, including logK1(NH3) = 4.0 for In(III). DFT calculations are used to obtain ΔE for the reaction [M(H2O)6]n+ + NH3 ⇆[M(H2O)5NH3]n+ + H2O for M(II) through M(IV) ions in water, represented as a structureless medium with the dielectric constant of water. Correlations are found that support the predicted value of logK1(NH3) for In(III) of 4.0. The nature of the intercepts on such correlations are discussed.
Group 11 Complexes with the Bidentate (SePPh2)2CH2 and Tridentate [(SePPh2)2CH]– Ligands
Authors: Canales Silvia , Crespo Olga , Gimeno M. Concepcíon , Jones Peter G. , Laguna Antonio
Published: February 2015

The reaction of (SePPh2)2CH2 with group 11 metal complexes such as [Au(C6F5)3(tht)] (tht = tetrahydrothiophene) affords the complex [Au(C6F5)3(SePPh2CH2PPh2Se)] in which the ligand coordinates to the gold(III) center only through one selenium atom. The treatment of the ligand with Ag(OTf) or [Cu(NCMe)4]PF6 leads, depending on the molar ratio, to the complexes [Ag2{(SePPh2)2CH2}2](OTf)2 or [M{(SePPh2)2CH2}2]X (M = Ag, X = OTf; M = Cu, X = PF6; OTf = CF3SO3) in which the phosphine selenide ligand coordinates as a bidentate bridging or chelating ligand through the Se,Se atoms. The reaction of (SePPh2)2CH2 with [Au(C6F5)2(acac)] (acac = acetylacetonate) occurs with deprotonation of the methylene group, and the methanide complex, [Au(C6F5)2(SePPh2CHPPh2Se)], is obtained, with a bidentate chelate Se,C coordination to the gold(III) center. The selenium atom can react further with other metal complexes such as [Au(C6F5)3(tht)] to give the dinuclear species [Au(C6F5)2{SePPh2CHPPh2SeAu(C6F5)3}], in which the ligand coordinates in a tridentate Se,C,Se form. The crystal structure of [Au(C6F5)2{SePPh2CHPPh2SeAu(C6F5)3}] has been established by X-ray diffraction.
On the Reaction of C(PPh3)2 with [Co2(CO)8]: Formation and Structure of an Unusual Tetranuclear Cluster
Authors: Petz Wolfgang , Wenck Kirstin , Neumüller Bernhard
Published: February 2015

The reaction of the carbodiphosphorane C(PPh3)2 (1) with [Co2(CO)8] results in the formation of the salt-like complex (HC{PPh3}2)[Co(CO)4] (2) in high yield if THF is used as the solvent. The proton of the cation stems from THF degradation. When the reaction is carried out in toluene, the tetranuclear cluster [Co4(CO)10(PPh3)(μ4-CCPPh3)] (3) is formed in low yield as the only complex which could be identified by X-ray analysis. The solvate 3 ·C7H8 crystallizes in the triclinic space group P1̄ with a = 1040.8(2), b = 1387.4(2), c = 1923.0(2) pm, α = 71.96(1)°, β = 88.69(1)°, γ = 71.46(1)°, Z = 2. The structure of the cluster with 64 CVE is that of a “spiked triangle” in which the triphenylphosphonioacetylide CCPPh3 acts as a six-electron donor and the bonding mode is that of a μ4-η2 coordination.
Synthesis and Luminescence Properties of [Pt{4-(o-MeC6H4)- pzbipy}Cl]SbF6 [pzbipy = 6-2''-pyrazinyl)-2,22'-bipyridine]
Authors: Field John S. , Gertenbach Jan-André , Haines Raymond J. , Munro Orde Q. , McMillin David R.
Published: February 2015

The synthesis and characterisation of the 4-(o-R-C6H4)pzbipy [R = H, CH3 or CF3; pzbipy = 6-(2″- pyrazinyl)-2,2′-bipyridyl] ligands are described. Reaction of the 4-(o-MeC6H4)pzbipy ligand with [Pt(PhCN)2Cl2] in the presence of AgSbF6 affords [Pt{4-(o-MeC6H4)pzbipy}Cl]SbF6 as a marooncoloured microcrystalline solid. The [Pt{4-(o-MeC6H4)pzbipy}Cl]+ cation exhibits low intensity photoluminescence in dichloromethane that maximises at 543 nm and which is assigned to a 3MLCT excited state (τ = 20 ns). The emission spectrum of the cation was also recorded in a frozen DME {1 : 5:5 (v/v) DMF / MeOH / EtOH} glass; a highly structured band is observed with vibrational spacings of ca. 1400 cm−1, indicating emission from an intraligand 3π-π∗ state (τ = 11 μs). Variable temperature solid emission spectra show maxima that occur at significantly lower energies than is observed in fluid solution and that shift to the red when the temperature is lowered; specifically, λ (em)max is 674 nm at 280 K (τ = 80 ns) and 723 nm at 80 K (τ = 1.3 μs). Emission behaviour of this type is typical of emission from a metal-metal-ligand charge transfer (MMLCT) excited state that has its origins in dz² (Pt)-dz² (Pt) orbital interactions in the crystal.
Der erste verbrückte, bifunktionelle Cyclopentadienyl-Imidazolyliden- Ligand und Komplexe mit Titan und Zirconium / The First Bridged, Bifunctional Cyclopentadienyl-Imidazolylidene Ligand and Complexes with Titanium and Zirconium
Authors: Müller Jörn , Piotrowski Ingo , von Chrzanowski Lars
Published: February 2015

Starting from imidazole, 1-[2-(cyclopenta-2,4-dienyl)ethyl]-3-methylimidazolium iodide (3) was obtained as a mixture of isomers by a simple three-step synthesis. The reaction of 3 with Ti(NEt2)4 or Zr(NEt2)4 by double deprotonation of the imidazolium salt led to the isomerically pure cationic complexes [{η5-C5H4-(CH2)2-NHC}M(NEt2)2]+I− (NHC = N-heterocyclic carbene) 4a (M = Ti) and 4b (M = Zr), respectively, in which a cyclopentadienyl and a methylimidazol-2-ylidene unit are linked by an ethylidene-1,2 bridge to form a novel chelating ligand system. In the case of the reaction of 3 with Zr(NEt2)4 the neutral compound [{η5-C5H4-(CH2)2-NHC}Zr(NEt2)I2] (5) is formed as an additional product. According to the X-ray structure analyses, the titanium atom of 4a is tetracoordinated while no coordinative interaction exists with the iodide anion; on the other hand, in 5 the zirconium centre is pentacoordinated.
β-Hydroxydithiozimtsäurederivate als Liganden. Synthese und Charakterisierung neuartiger 1,1-Ethendithiolato- und O,S-Chelatkomplexe / Derivatives of β -Hydroxydithiocinnamic Acids as Ligands. Syntheses and Characterisation of Novel 1,1-Ethenedithiolato and O,S-Chelate Complexes
Authors: Schubert Karsten , Görls Helmar , Weigand Wolfgang
Published: February 2015

Starting from 4-bromoacetophenone 1, the 4-bromo-β -hydroxydithiocinnamic acid 2 and the 4-bromo-β -hydroxydithiocinnamic acid hexyl ester 3 were prepared using carbon disulfide and potassium-tert-butylate as a base. Acting as a ligand, the acid gives 1,1-ethenedithiolato complexes with (Ph3P)2Pt(II) (4a), (Et3P)2Pt(II) (4b), dppePt(II) (4c), (Ph3P)2Pd(II) (4d), dppePd(II) (4e), and dppeNi(II) (4f). In contrast to the acid, the deprotonated ester 3 forms a monoanionic bidentate ligand. [O,S] Complexes of Pt(II) (5a), Pd(II) (5b) and Ni(II) (5c) were obtained. All complexes have been fully characterised using 1H NMR, 13C NMR and 31P NMR spectroscopy, mass spectrometry, infrared spectroscopy and elemental analyses. The molecular structures of the complexes 4b and 5a - 5c were determined by X-ray diffraction analyses.
Synthesis, Characterisation and Crystal Structure of a Copper(II) Dichromate Complex with the N,N’-Bis(2-pyridylmethylene)butane- 1,4-diamine Schiff Base Ligand
Authors: Samanta Brajagopal , Chakraborty Joy , Shit Shyamapada , Batten Stuart R. , Jensen Paul , Mitra Samiran
Published: February 2015

The new complex Cu[L1]Cr2O7has been synthesised with the N,N′-bis(2-pyridylmethylene) butane-1,4-diamine Schiff base L1, [NC5H4CH=N(CH2)4N=CHC5H4N], and characterised with elemental analyses and different spectroscopic and electrochemical studies. The structure of the new complex has been established by single crystal X-ray diffraction. The complex crystallises in the monoclinic system with space group P21/c having cell parameters a = 14.7(5), b = 9.22(2), c = 16.2(5) Å , β = 116.9(1)°, and Z = 4. The Cr2O7
2− unit is bonded through one terminal oxygen donor end to the central Cu(II) chelated by the Schiff base ligand.
Carbamoyl Derivatives of a Pyridine-Based Tetraamine
Authors: K. Bilakhiya Anvarhusen , Heinemann Frank W. , Grohmann Andreas
Published: February 2015

The reaction of four equivalents of phenyl or tert-butyl isocyanate with the pyridine-derived tetraamine 2,6-C3H3N[CMe(CH2NH2)2]2 in toluene gives high yields of the quadruply ureido substituted products 2,6-C5H3N[CMe(CH2R)2]2 [R = -NH(CO)NHPh and -NH(CO)NHtBu]. Full spectroscopic data for both compounds are given. A single crystal X-ray structure determination of the phenyl derivative reveals an intricate network of both intra- and intermolecular hydrogen bonds involving the C=O and both NH functionalities in all ureido groups.
Efficient Asymmetric Synthesis of Prostaglandin E1
Authors: Jung Jae-Chul , Park Oee-Sook
Published: February 2015

A simple synthesis of prostaglandin E1 (PGE1) is described. The key steps are an asymmetric Michael addition to establish the desired (R)-configurations at C8 and C12 of the 2- (trimethylsilyl)ethoxymethyl- (SEM) protected PGE1 and its one-pot deprotection with magnesium bromide in high yield. This method is potentially useful for the preparation of other modified prostaglandins.
TMC-151 A Monoacetate, a New Polyketide from Bionectria ochroleuca
Authors: Jua Yu-Ming , Juang Shin-Hun , Chen Ke-Jun , Lee Tzong-Huei
Published: February 2015

A new polyketide, TMC-151 A monoacetate (1), along with a known analogue, TMC-151 F (2), was isolated from ethyl acetate extracts of the fermentation broth of Bionectria ochroleuca isolated in Taiwan. Their structures were elucidated on the basis of spectroscopic analysis. The antiproliferative activities of 1 and 2 were evaluated against MT-2 (human leukemia), A498 (human renal carcinoma), NPC-tw01 (human nasopharyngeal carcinoma), H-226 and A549 (non-small cell lung cancer) cell lines, and their IC50 values ranged from 18.3 to 40.2 μM.
Laurentixanthone C: A New Antifungal and Algicidal Xanthone from Stem Bark of Vismia laurentii
Authors: Tala Michel F. , Krohn Karsten , Hussain Hidayat , Kouamc Simeon F. , Wabo Hippolyte K. , Tane Pierre , Schulz Barbara , Hu Qunxiu
Published: February 2015

Laurentixanthone C (1), a new xanthone, was isolated from the stem bark of Vismia laurentii (Guttiferae or Clusiaceae), in addition to the known compounds vismiaquinone (2), bisvismiaquinone (3), and dammaradienol (4). The structures were established based on spectroscopic studies, notably of the 2D NMR spectra. Preliminary results showed that 1 is algicidal and strongly antibacterial against the Gram-positive bacteria Bacillus megaterium and Chlorella fusca, respectively.
A Novel Norditerpene from Eupatorium adenophorum
Authors: Wang Ming-Zhong , Cai Xiang-Hai , Du Guo-Shun , Luo Xiao-Dong
Published: February 2015

A novel norditerpene was isolated from the flower of Eupatorium adenophorum, named (4aR,7R,8S,8aR)-1,2,4a,5,6,7,8,8a-octahydro-8-[3-methylenebut-4-alyl]-4,4a,7,8-tetramethylnaphthalen- 2(1H)-one (1). Its structure was established by extensive NMR experiments. Based on the diversity of the side chains, a possible biodegradation pathway for the compound from the clerodane skeletone is proposed.
Two New Leucosesterterpenes from Leucosceptrum canum
Authors: Choudhary Muhammad Iqbal , Ranjit Rosa , Rahman Atta-ur , Devkota Krishna Prasad , Shrestha Tirtha Maiya
Published: February 2015

Two new sesterterpenes, 14β -methylleucosesterterpenone (1) and 17α-hydroxyleucosceptrine (2), along with a known triterpene, hypoglauterpenic acid (6), were isolated from the Leucosceptrum canum of Nepalese origin. The structures were elucidated on the basis of spectroscopy techniques.
MS-guided Fractionation as a Fast Way to the Identification of New Natural Products – MALDI-TOF-MS Screening of the Marine Sponge Stylissa caribica
Authors: Grube Achim , Maier Thomas , Köck Matthias
Published: February 2015

MALDI-TOF-MS was used for the first time as a direct screening method to analyse sponge tissue (Stylissa caribica). In order to validate this method the results were compared with a HPLC-ESI-MS analysis of the crude extract from the investigated sponge. Both methods showed a good agreement in their results, allowing for the rapid identification of 15 pyrrole-imidazole alkaloids.
Synthesis and X-Ray Crystal Structure of Two Novel Ester Ferrocenophanes
Authors: Tao Li , Bingqin Yang , Bo Gao
Published: February 2015

Two novel ester ferrocenophanes have been prepared by esterification of 1,1′-ferrocenedi(carbonyl chloride) with glycol and 1,4-butanediol, respectively. Both of them have been characterized by IR, elemental analysis, MALDI-TOF MS and 1H NMR spectroscopic methods, and their structures have been elucidated by X-ray diffraction. The intermolecular associations based on C-H···O hydrogen bonds have also been discussed. These molecules are assembled into chains, and the chains are further assembled into a 3D structure through several hydrogen bonds.
Preparation of a Copper(I) Halide Coordination Polymer by Thermal Decomposition of a Precursor with Predefined Stoichiometry
Authors: Jeß Inke , Näther Christian
Published: February 2015

The ligand-rich precursor compound tetra-μ-chloro-bis (μ2-2,3-dimethylpyrazine)-tetrakis-(acetonitrile-N)tetracopper(I) (1) was prepared by the reaction of CuCl with 2,3-dimethylpyrazine in acetonitrile. On heating this compound decomposes quantitatively in a single step directly to the ligand-deficient coordination polymer di-μ3-chloro-(μ2-2,3-dimethylpyrazine-N,N′)copper(I).
RE2+xI2M2+y (RE = Ce,Gd, Y; M = Al, Ga): Reduced Rare Earth Halides with a Hexagonal Metal Atom Network
Authors: Lukachuk Mar’yana , Zheng Chong , Mattausch Hansjürgen , Kremer Reinhard K. , Simon Arndt , Banks Michael G.
Published: February 2015

The title compounds were synthesized from RE, REI3 (RE = Ce, Gd, Y) and Al or Ga under an Ar atmosphere at 930 - 950 °C. The non-stoichiometric Ce2+xI2Al2+y and Ce2+xI2Ga2+y compounds crystallize in the space group R3̄m (No. 166) with lattice constants a = 4.3645(3), c = 35.914(2) Å for the Al and a = 4.3009(2), c = 35.680(4) Å for the Ga compound. Excess electron density found in the Wyckoff position 3a could be due to a fractional occupation by Ce or M (x = 0.06, y = 0 or x = 0, y = 0.11 in the case of the Ga compound). The stoichiometric Gd2I2Ga2 and Y2I2Ga2 compounds crystallize in the space group P3̄m1 (No. 164) with lattice constants a = 4.1964(1) and 4.1786(7) Å , c = 11.4753(4) and 11.434(2) Å , respectively. Their structures feature M-centered (M = Al, Ga) RE trigonal prisms condensed via common rectangular faces. The electronic origin of the surplus of metal atoms in the octahedral voids between the I-layers of the Ce compounds was explored via extended Hückel-type calculations. Magnetic susceptibility, electrical resistivity and heat capacity measurements have also been carried out. These reveal a metal-insulator transition of Gd2I2Ga2 at 40 K.
Structure and Properties of α- and β-CeCuSn: A Single Crystal and Mössbauer Spectroscopic Investigation
Authors: Sebastian C. Peter , Rayaprol Sudhindra , Hoffmann Rolf-Dieter , Rodewald Ute Ch. , Pape Tania , Pöttgen Rainer
Published: February 2015

Two modifications of CeCuSn were prepared from the elements: the high-temperature (β ) modification crystallizes directly from the quenched sample, while the low-temperature (α) modification is formed after annealing at 700 °C for one month. Both modifications were investigated by powder and single crystal X-ray diffraction. We find for β -CeCuSn the ZrBeSi-type structure, space group P63/mmc, a = 458.2(1), c = 793.7(2) pm, wR2 = 0.0727, 148 F2 values, 8 variable parameters. In the case of α-CeCuSn we find the NdPtSb-type structure, space group P63mc, a = 458.4(1), c = 785.8(2) pm, wR2 = 0.0764, 233 F2 values, 11 variable parameters. The copper and tin atoms build up layers of ordered [Cu3Sn3] hexagons. The layers are planar in β -CeCuSn, however, with highly anisotropic displacements of the copper and tin atoms. In α-CeCuSn a puckering effect is observed resulting in a decrease of the c lattice parameter. Both modifications of CeCuSn exhibit antiferromagnetic ordering, but there is a considerable difference in their magnetic behaviour. Anomalies in the physical properties of the α- and β -modifications of CeCuSn have been detected by Mössbauer spectroscopy and magnetic and specific heat measurements, which serve to explain the structure-property relations.
Das Koordinationsverhalten des Acetylendisulfids Bis(benzylthio)acetylen gegenüber nullwertigen Metallkomplexen des W, Co und Pt/The Coordination Behavior of the Acetylenedisulfide Bis(benzylthio)acetylene with Zero-valent Metal Complexes of W, Co and Pt
Authors: Seidel Wolfram W. , Meel Matthias J. , Lügger Thomas
Published: February 2015

Synthesis and characterization of the alkyne complexes [Co2(CO)6(L)], [W(CO)(L)3] and [Pt(PPh3)2(L)] with L = BnSC2SBn (Bn = benzyl) are described. X-Ray diffraction studies of [W(CO)(L)3] and [Co2(CO)5(L)]2 reveal that the donor ability of the sulfide group depends on the electronic and steric situation in the particular metal complex. The specific donor strength of sulfidesubstituted alkynes in their complexes is discussed considering the IR and NMR spectroscopic data.
Some New Nickel 1,2-Dichalcogenolene Complexes as Single-component Semiconductors
Authors: Papavassiliou George C. , Anyfantis George C. , Steele Barry R. , Steele Barry R. , Terzis Aris , Raptopoulou Catherine P. , Tatakis George , Chaidogiannos George , Glezos Nikos , Weng Yufeng , Yoshino Harukazu , Murata Keizo
Published: February 2015

The complexes Ni(dmeds)(dmit), Ni(dmedt)(dmit), Ni(dpedt)(dsit), Ni(dpedt)(dmit), and Ni(dcdt)(dmit) (where dmeds is dimethylethylenediselenolate, dmedt is dimethylethylenedithiolate, dpedt is diphenylethylenedithiolate, dcdt is 1,2-bis-decylsulfanyl-ethene-1,2-dithiolate, dmit is 1,3-dithiol-2-thione-4,5-dithiolate, and dsit is 1,3-dithiol-2-thione-4,5-diselenolate) were prepared and characterized. The new complexes exhibit semiconducting behavior, with band gap values around 0.8 eV.
Charge Density of L-Alanyl-glycyl-L-alanine Based on X-Ray Data Collection Periods from 4 to 130 Hours
Authors: Förster Diana , Wagner Armin , Hübschle Christian B. , Paulmann Carsten , Luger Peter
Published: February 2015

The charge density of the tripeptide L-alanyl-glycyl-L-alanine was determined from three X-ray data sets measured at different experimental setups and under different conditions. Two of the data sets were measured with synchrotron radiation (beamline F1 of Hasylab/DESY, Germany and beamline X10SA of SLS, Paul-Scherer-Institute, Switzerland) at temperatures around 100 K while a third data set was measured under home laboratory conditions (MoKα radiation) at a low temperature of 20 K. The multipole refinement strategy to derive the experimental charge density was the same in all cases, so that the obtained charge density properties could directly be compared. While the general analysis of the three data sets suggested a small preference for one of the synchrotron data sets (Hasylab F1), a comparison of topological and atomic properties gave in no case an indication for a preference of any of the three data sets. It follows that even the 4 h data set measured at the SLS performed equally well compared to the data sets of substantially longer exposure time.
Syntheses and Structures of 9-Bromo-10-diphenylphosphanylanthracene and its Oxidation Products
Authors: Schwab Gerald , Stern Daniel , Leusser Dirk , Stalke Dietmar
Published: February 2015

Treatment of 9,10-dibromoanthracene with one mole equivalent of n-butyllithium and chlorodiphenylphosphane yields 9-bromo-10-diphenylphosphanylanthracene (1). Oxidation of 1 with chalcogens leads to {Br(C14H8)(Ph2P=E)} with E = O (2), S (3) and Se (4). The syntheses and structure determinations of the parent compound 1 and the oxidized species 2 - 4 are reported.
Synthesis and Spectral Characterization of Hydrazone Schiff Bases Derived from 2,4-Dinitrophenylhydrazine. Crystal Structure of Salicylaldehyde-2,4-Dinitrophenylhydrazone
Authors: Monfared Hassan Hosseini , Pouralimardan Omid , Janiak Christoph
Published: February 2015

Reactions of 2,4-dinitrophenylhydrazine with salicylaldehyde, pyridine-2-carbaldehyde and 2- aminobenzophenone in methanol result in the hydrazone Schiff base ligands salicylaldehyde-, pyridine- 2-carbaldehyde-, and 2-aminobenzophenone-2,4-dinitrophenylhydrazone, respectively. Crystals of salicylaldehyde-2,4-dinitrophenylhydrazone are monoclinic, space group P21/c, a = 13.820(3), b = 4.3515(9), c = 25.159(7) Å , β = 123.01(2)° with Z = 4. The molecular packing is mostly a zigzag or herring-bone pattern.
A Convenient Procedure for the Preparation of Sulfonamidoureas Using Triphosgene
Authors: Safaei-Ghomi Javad , Bamoniri Abdolhamid , Abbaszadeh-Nooshabady Aboalfazl
Published: February 2015

An efficient method for the preparation of sulfonamidourea using triphosgene in organic solvents is reported.Sulfonylhydrazides and acetylsulfanilylhydrazide were transformed into the corresponding intermediates using triphosgene in 1,4-dioxane/water or tetrahydrofuran as solvents.These intermediates were converted in situ into symmetrical and unsymmetrical sulfonamidoureas in high yields and shorter periods of time related to previous methods.
Triterpenoid Saponins from Metadina trichotoma
Authors: Zhang Yu-Mei , Tan Ning-Hua , Huang Huo-Qiang , Zeng Guang-Zhi
Published: February 2015

Two new 27-nor-triterpene glycosides, pyrocincholic acid 3β -O-β -D-glucopyranosyl-(1→4)- β -D-quinovopyranosyl-28-O-β -D-glucopyranoside (Metatrichoside A, 1), pyrocincholic acid 3β -O-β -D-glucopyranosyl-(1→4)-β -D-quinovopyranosyl-28-O-β -D-glucopyranosyl-(1→6)-β -Dglucopyranoside (Metatrichoside B, 2), together with pyrocincholic acid 3β -O-β -D-quinovopyranosyl- 28-O-β -D-glucopyranoside (3), pyrocincholic acid 3β -O-β -D-quinovopyranosyl-28-O-β -Dglucopyranosyl-( 1→6)-β -D-glucopyranoside (4), quinovic acid 3β -O-β -D-quinovopyranoside (5), quinovic acid 3β -O-β -D-quinovopyranosyl-28-O-β -D-glucopyranoside (6), quinovic acid 3β -O- β -D-glucopyranoside (7) and quinovic acid 3β -O-β -D-glucopyranosyl-28-O-β -D-glucopyranoside (8) were isolated from the barks of Metadina trichotoma. Their structures were mainly determined by mass spectrometric and 1D and 2D NMR spectroscopic methods. Compound 5 and 6 showed cytotoxic activities towards the A549 non-small-cell lung cancer cell line (IC50 = 8.43 and 6.06 μm), and the methanol extract inhibited the activity of cathepsin B with an IC50 value of 0.77 μg mL−1.
Two New Iridoid Glycosides from Lagotis yunnanensis
Authors: Yang Xiao-Dong , Yang Li-Juan , Yang Shu , Zhao Jing-Feng , Zhang Hong-Bin , Li Liang
Published: February 2015

Two new iridoid glycosides, named lagotisoside D (1) and E (2), were isolated from Logatis yunnanensis. The structures of the two compounds were established as 6-O-α-L-(4″-O-E-3‴,4‴-dimethoxycinnamoyl) rhamnopyranosylcatalpol (1) and 6-O-α-L-(4″-O-Z-3‴,4‴-dimethoxycinnamoyl) rhamnopyranosylcatalpol (2) on the basis of spectral analysis.
Syntheses And Structural Characterizations Of Heterometallic Copper(I)/Indium(Iii) Complexes Containing Phosphine Ligands
Authors: Zhang Xiu-Zhen , Song Yan-Wei , HuiWu Fang , Zhang Qian-Feng
Published: February 2015

Addition of anhydrous InCl3 to a THF solution of CuCl and dppe (dppe = Ph2PCH2CH2PPh2), or CuCl and PPh3, resulted in the formation of the crystalline heterometallic copper(I)/indium(III) complexes [(dppeCu)2(μ-Cl)(μ-dppe)][InCl4]·THF (1·THF) and [{Cu(PPh3)2}2(μ-Cl)4(InCl)]·THF (2·THF), respectively, which have been characterized by X-ray diffraction. Compound 1 is composed of a dinuclear copper(I) complex cation and a mononuclear tetrahedral indium(III) complex anion. Complex 2 comprises an indium center in a quasi square-pyramidal chloride-coordination environment connected to two Cu(PPh)3 fragments via Cu(μ-Cl)2 In bridges
Substitutionsreaktionen An Alkinkomplexen Des Nb(Iii) Und Mo(Ii) Mit Dem Liganden Bis(Benzylthio)Acetylen
Authors: Seidel Wolfram W. , Schaffrath Markus , Meel Matthias J. , Hamilton Tracy , Ariza Susana Castelar , Pape Tania
Published: February 2015

Substitution reactions of the bis(benzylthio)acetylene complexes [Tp′Nb(BnSC2SBn)Cl2] and

[Tp′Mo(BnSC2SBn)(CO)2](PF6) (Tp′ = hydro-tris(3,5-dimethyl)pyrazolylborate, Bn = benzyl)

have been investigated. The coordination of the alkyne ligand turned out to be very stable,

while one chloride ion in [Tp′Nb(BnSC2SBn)Cl2], and either one or both of the CO ligands

in [Tp′Mo(BnSC2SBn)(CO)2](PF6) can be substituted. The dissociative mechanism of the reactions

with [Tp′Mo(BnSC2SBn)(CO)2](PF6) and [Tp′ Mo(BnSC2SBn)(CO)Cl] leads to the primary

and exclusive reaction with the solvent. In the course of these studies the structures

of [Tp′Nb(BnSC2SBn)Cl2], [Tp′Mo(BnSC2SBn)(CO)(MeCN)](PF6), [Tp′Mo(BnSC2SBn)(CO)Cl]

and [Tp′Mo(BnSC2SBn)Cl2][Tp′Mo(BnSC2SBn)ClF] have been determined by X-ray diffraction.

Comparison of the closely related compounds allows conclusions how the number of d electrons and

the character of the co-ligands influence the alkyne bonding
Syntheses, Spectroscopy And Crystal Structures Of (R)-N-(1-Aryl-Ethyl)Salicylaldimines And [Rh{(R)-N-(1-Aryl-Ethyl)Salicylaldiminato}(η4-Cod)] Complexes
Authors: Enamullah Mohammed , Uddin A.K.M. Royhan , Chamayou Anne-Christine , Janiak Christoph
Published: February 2015

Condensation of salicylaldehyde with enantiopure (R)-(1-aryl-ethyl)amines yields the enantiopure Schiff bases (R)-N-(1-aryl-ethyl)salicylaldimine (HSB*; aryl = phenyl, 2-methoxyphenyl, 3- methoxyphenyl, 4-methoxyphenyl (4), 4-bromophenyl (5), 2-naphthyl). These Schiff bases readily react with dinuclear (acetato)(η4-cycloocta-1,5-diene)rhodium(I), [Rh(μ-O2CMe)(η4-cod)]2, to afford the mononuclear complexes, cyclooctadiene-((R)-N-(1-aryl-ethyl)salicylaldiminato-κ2N,O)- rhodium(I), [Rh(SB∗)(η4-cod)] (SB* = deprotonated chiral Schiff base = salicylaldiminate; aryl = phenyl (7), 2-methoxyphenyl, 4-methoxyphenyl, 4-bromophenyl, 2-naphthyl). The complexes have been characterized by IR, UV/vis, 1H/13C NMR and mass spectrometry, optical rotation as well as by single-crystal X-ray structure determination for 4, 5 and 7. The structure of 5 shows C-Br· · ·π contacts. Compound 7 is only the second example of a Rh(η4-cod) complex with a six-membered Rh-N,O-chelate ring
Syntheses, Spectral, Thermal And Structural Characterization Of 2-Hydroxyanilinium And 2-Amino-3-Hydroxy-Pyridinium Squarates
Authors: Zafer Okan , Paşaoğlub Hümeyra , Yılan O. Ozan , Büyükgüngör Orhan
Published: February 2015

New salts of 2-hydroxyaniline and 2-amino-3-hydroxypyridine with squaric acid were synthesized and characterized by elemental analyses, IR spectroscopy and thermal analyses (TG, DTG and DTA). The crystal structures of bis(2-hydroxyanilinium) squarate, [(C6H8NO+)2(C4O4)2−] (1) and bis(2- amino-3-hydroxy-pyridinium) squarate dihydrate, [(C5H7N2O+)2(C4O4)2−] · 2 H2O (2) were determined by single crystal X-ray diffraction. Both compounds crystallize in the monoclinic system, space group P21/c. The organic ammonium squarates decompose in two thermal steps
Reaktionsbeteiligung Von Oximfunktionen Bei Der Dehydrierung Von 2-Phenylpiperidin-Derivaten
Authors: Möhrle Hans , Gehlen Michael
Published: February 2015

Mercury(II)-induced dehydrogenation of α-(2-phenylpiperidin-1-yl)-acetophenone oximes 7 gives rise to two different iminium compounds which subsequently react with the neighbouring oxime group. With the mercury(II)-EDTA reagent, (E)-7 forms the cyclic nitrones 9 and 11a, b, whereas (Z)-7 is transformed into oxadiazines 12 and 13a, b. The pairs of diastereomers 11a, b and 13a, b result from the equilibrium involving an iminium oximate species. The introduction of electron donor or acceptor groups into the phenyl substituent in (E)-15 and (E)-16 does not influence significantly the direction of dehydrogenation. With mercury(II) acetate in dilute acetic acid no specifity of the oxime configuration is observed, and the nitrones and oxadiazines are produced together. This may be explained by a reaction with the acetate ion at the iminium oxime stage. NMR experiments in CDCl3 have shown that treatment of nitrone 2 and oxadiazine 3 with CF3COOD causes ring cleavage by prototropy and after longer reaction times generates the same imidazole 23
Synthesis And Structural Characterization Of 1-Butyl-2,3-Dimethylimidazolium Bromide And Iodide
Authors: Kutuniva Johanna , Oilunkaniemi Raija , Laitinen Risto S. , Asikkala Janne , Kärkkäinen Johanna , Lajunen Marja K.
Published: February 2015

1-Butyl-2,3-dimethylimidazolium bromide {(bdmim)Br} (1) and iodide {(bdmim)I} (2) were prepared conveniently by the reaction of 1,2-dimethylimidazole and the corresponding 1-halobutane. The compounds were characterized by 1H and 13C{1H} NMR spectroscopy as well as by X-ray single crystal crystallography. 1 crystallizes in the monoclinic crystal system, space group P21/n, with Z = 4, and unit cell dimensions a = 8.588(2), b = 11.789(1), c = 10.737(2) Å, β = 91.62(3)°. Compound 2 crystallizes in the monoclinic crystal system, space group P21/c, with Z = 8, and unit cell dimensions a = 10.821(2), b = 14.221(3), c = 15.079(2) Å , β = 90.01(3)°. The lattices of the salts are built up of 1-butyl-2,3- dimethylimidazolium cations and halide anions. The cations of 1 form a double layer with the imidazolium rings stacked together due to π interactions. The Br− anions lie approximately in the plane of the imidazolium ring, and the closest interionic Br···H contacts span a range of 2.733(1) - 2.903(1) Å. Compound 2 shows no π stacking interactions. The closest interionic I···H contacts are 2.914(1) - 3.196(1) Å
Single Crystal Investigation and Physical Properties of the Binary Compound CeB4
Authors: Babizhetskyy Volodymyr , Simon Arndt , Hiebl Kurt
Published: February 2015

The structure of CeB4 has been determined by single crystal X-ray diffraction. The compound crystallizes in the ThB4 structure type (space group P4/mbm, a = 7.2034(8), c = 4.1006(5) Å; 270 reflections with Fo ≥ 4σ (Fo), R1 = 0.023, wR2 = 0.052). The results of the magnetic and electrical resistivity measurements indicate a strong f-d hybridization of the 4 f electrons of the cerium atom
Magnetic Properties of Polycrystalline PrCu2: A Quadrupolar Transition Material
Authors: Fernández Jesús Rodríguez
Published: February 2015

Polycrystalline PrCu2, which has a quadrupolar transition at 7.7 K, has been investigated using electrical resistivity, magnetization and dilatometry techniques. To study dilution effects, two solid solutions of PrCu2, (Pr0.8La0.2)Cu2, and (Pr0.8Y0.2)Cu2, were also studied. The quadrupolar transition decreases in temperature with doping, while it increases slightly with the magnetic field. In resistivity and thermal expansion, the magnetic contributions show a clear evidence of crystal field excitations. The analysis of both properties provided benchmark values of the Debye temperature and Grüneisen parameters.
Solid State and Electronic Structure of Rare Earth Metal Intercalated Graphite from First-principles Theory
Authors: Fang Chang-Ming , Bauer Joseph , Saillard Jean-Yves , Halet Jean-Francois
Published: February 2015

The structural arrangements of the graphite intercalates LnC6 (Ln = La, Ce, Nd and Yb) were investigated using Density Functional Theory (DFT) within the Generalized Gradient Approximation (GGA). The EuC6-type structure (AαAβ AαAβ AαA stacking) is slightly energetically preferred for La and Ce, whereas with the other rare earth metals almost the same cohesive energies are found for the three different atomic arrangements AαAαAαAαAαA. . ., AαAβ AαAβ AαA. . ., and AαAβ AγAαAβ A. . . A rather important charge transfer occurs from the metals to the carbon sheets, with the electrons partially occupying the bottom of the carbon π* band. As a consequence, a lengthening of the C-C bond lengths of ca. 0.02 Å is computed with respect to the C-C bonds in graphite. Two-dimensional metallic character is expected for LaC6 according to its band structure.
Catalytic Ring Opening of α-Epoxyketones Using DDQ in Methanol Solution at Room Temperature and under Reflux Conditions in Excellent Yields
Authors: Memarian Hamid R. , Saffar-Teluri Ali , Khosravi-Babadi Mohsen
Published: February 2015

Catalytic ring opening reactions of α-epoxyketones by 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) in methanol solution at r. t. and under reflux conditions resulted in the formation of α-hydroxy-β -methoxyketones through Cβ -O bond cleavage in excellent yields.Whereas the type and nature of the additional substituent affects the rate of ring opening, the effect of temperature has an extreme influence on the rate of reactions. Cyclic voltammetric studies of DDQ at 15 °C and 33 °C support the increased electron-acceptor ability of DDQ by the increasing of temperature.
Die Kristallstrukturen von Ni(AlCl4)2, Ni(GaCl4)2 und Na[Ni(AlCl4)3] / Crystal Structures of Ni(AlCl4)2, Ni(GaCl4)2 and Na[Ni(AlCl4)3]
Authors: Keßler Ulrich , Müller Rainhard
Published: February 2015

The crystal structures of Ni(AlCl4)2, Ni(GaCl4)2 and Na[Ni(AlCl4)3] were determined by single crystal X-ray structure analysis. Ni(AlCl4)2 and Ni(GaCl4)2 are isotypic and crystallize in the Co(AlCl4)2 structure type (I2/c, a = 1276.40(9)/1268.48(7), b = 771.41(5)/757,74(3), c = 1145.47(8)/1154.34(7) pm, β = 92.067(3)/91.778(4)°, Z = 4). The structure contains chains of NiCl6 octahedra and AlCl4/GaCl4 tetrahedra linked by corners and edges. Na[Ni(AlCl4)3] represents a new structure type (P21/c, a = 1356.34(6), b = 1200.82(6), c = 1213.31(6) pm, β = 105.647(6)°, Z = 4). Its characteristic feature is the chiral [Ni(AlCl4)3]− anion which is found here for the first time. The tetrachloroaluminate ions serve as bidentate ligands leading to an octahedral coordination of the nickel atom.
Ba5Al2Ge7 und Ba7Al4Ge9: Zwei neue intermetallische Phasen mit ungewöhnlichen Al-Ge-Anionen / Ba5Al2Ge7 and Ba7Al4Ge9: Two New Intermetallic Phases with Unusual Al-Ge Anions
Authors: Wendorff Marco , Röhr Caroline
Published: February 2015

In the ternary system Ba-Al-Ge new intermetallic compounds which are lying on or close to the binary section BaAl2 -BaGe2 were synthesized from the elements and characterized on the basis of X-ray single crystal data. The Al-content x in the compounds BaAlxGe2−x forming the AlB2 structure type ranges from x = 1.4 [BaAl1.4Ge0.6 space group P6/mmm, a = 443.5(1), c = 512.4(1) pm, Z = 1, R1 = 0.0222] to the stoichiometric ordered compound BaAlGe [space group P6̅m2, a = 434.9(1), c = 513.6 pm, Z = 1, R1 = 0.0252]. In the two new Ge-rich barium intermetallics Ba5Al2Ge7 [space group C2/m, a = 859.8(4), b = 1031.5(4), c = 1847.8(6) pm, β = 103.23(3)°, Z = 4, R1 = 0.0553] and Ba7Al4Ge9 [space group Fmm2, a = 1032.7(5), b = 2559(2), c = 862.1(4) pm, Z = 4, R1 = 0.1197] complex Al/Ge polyanions are present, which consist of (1) Al/Ge-ribbons of condensed planar sixmembered rings comparable to the anions in Ba3Al2Ge2, and (2) [Ge/Al]5 clusters comparable to the anions in the tetrelides Ba3M5. The building units (1) and (2) are connected via Al-Ge bonds to form complex ribbons in the case of Ba5Al2Ge7 and sheets in the case of Ba7Al4Ge9. The electron count in the two compounds supports an interpretation of the structures according to the Zintl concept and the Wades rules. The small formal electron excess, caused by the incomplete transfer of charge from Ba towards the Al/Ge polyanions, decreases with the Ge content of the compound.
Synthesis and Structural Characterization of Bis(aziridine) Cobalt(II), Zinc(II) and Palladium(II) Complexes
Authors: Roedel J. Nicolas , Bobka Roman , Pfister Max , Rieger Martin , Neumann Bernd , Lorenz Ingo-Peter
Published: February 2015

The reactions of anhydrous metal chlorides MCl2 [M = Co(II), Zn(II), Pd(II)] with aziridines (az) in CH2Cl2 at r. t. in a 1 : 5 molar ratio afforded the bis(aziridine)dichloro complexes M(az)2Cl2. After purification, all complexes were fully characterized. The solid state structures were determined using single crystal X-ray diffraction, and showed tetrahedral coordination geometries for the Co(II) and Zn(II) centers and trans-configurated square planar geometries for Pd(II).
Note: Crystal Structure, Vibrational Spectrum and Thermal Behavior of the Ammonium Hexathiohypodiphosphate Dihydrate, (NH4)4P2S6 · 2H2O
Authors: Gjikaj Mimoza , Brockner Wolfgang
Published: February 2015

Single crystals of (NH4)4P2S6 ・ 2H2O could be obtained and the crystal structure determined (monoclinic, P21/c with a = 6.931(1), b = 12.730(2), c = 17.446(2) Å , β = 96.87(1)°, V = 1528.2(4) Å3, Z = 4). The NH4
+, and [P2S6]4− ions and the water molecules are involved in an extended hydrogenbonding network. The FT-Raman and FT-IR spectra have been recorded and the observed vibrational frequencies assigned to tetrahedral NH4
+ and [P2S6]4− (D3d) ions as well as to H2O molecules. The thermogravimetric analysis has shown that (NH4)4P2S6 · 2H2O starts to decompose at around 60 °C (up to 170 °C), but no distinct intermediates could be observed.
2D and 3D Silver(I)-Ethylenediamine Coordination Polymers with Ag–Ag Argentophilic Interactions
Authors: Dai Ji-Xiang , Zhu Hai-Liang , Rothenberger Alexander , Zhang Qian-Feng
Published: February 2015

Two complexes of silver(I) salts with ethylenediamine (etda) as a ligand were prepared and characterized. The study of the crystal structures (of the 2-hydroxy-4-nitro-benzoate trihydrate (1) and nitrate (2)) has shown that the formation of 2D and 3D coordination polymer networks results from etda ligands bridging the silver atoms which are connected via Ag-Ag argentophilic interactions.