bluuebunny/crossref_metadata_2025 huggingface dataset:
Crystal Structure of the Di-bromo-bis(2-dimethylaminoethanolato)(dimethylsulfoxide)-copper(II)-lead(II) Dimer Obtained by Direct Synthesis
Authors: Kovbasyuk Larisa A. , Vassilyeva Olga Yu. , Kokozay Vladimir N. , Linert Wolfgang
Published: February 2015

A heterotetranuclear CuIIPbII complex containing 2-dimethylaminoethanol has been synthesized, using copper powder and PbBn2 as starting materials, and characterized by X-ray crystallography. The crystal is composed of centrosymmetric molecules [CuPbBr2{(CH3)2NCH2CH2O}2dmso]2. The central strictly planar fragment is a Pb2O2 parallelogram completed by bridging oxygen atoms of chelating 2-dimethylaminoethoxo groups. The Pb atom forms four quite short bonds with oxygen atoms of the three 2-dimethylaminoethoxo groups and of the dmso molecule and assumes a six-coordinate structure also involving two bromine atoms. The two oxygen and two nitrogen atoms of two 2-dimethylaminoethoxo groups form the copper coordination environment, which possesses a somewhat distorted square planar geometry.
Monoheteroarylborate [1] / Monoheteroarylborates [1]
Authors: Kuhn Norbert , Kotowski Heike , Bläser Dieter , Boese Roland
Published: February 2015

The heteroaryl borates Li[C4Me4NBH3] (6) and Na[C3H3N2(BMe3)2]• 2 C4H8O (8) are ob­tained by treatment of Li[C4Me4N] and Na[C3H3N2] with Me2S • BH3 and BMe3, respectively. The X-ray structure of [Na(C4H8O)6][C3H3N2(BMe3)2] (10) is reported.
Synthese und Kristallstruktur eines Barium-Zink-Vanadyl-phosphats BaZn(VO)(PO4)2 mit [(VO)PO4]-Schichten / Synthesis and Crystal Structure of a Barium-Zinc-Vanadyl-Phosphate BaZn(VO)(PO4)2 Containing [(VO)PO4] Layers
Authors: Meyer S. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of BaZn (VO)(PO4)2 have been prepared by solid state reactions of prereacted BaCO3 and P2O5 mixtures with ZnO, V2O3 and V2O5 in evacuated quartz tubes. X-ray investigations led to orthorhombic symmetry, space group D2h
15 -Pbca, a = 8.814(1), b = 9.039(1), c = 18.538(1) A, Z = 8 . The crystal structure is characterized by layers of PO4 tetrahedra and square VO1+5 pyramids, connected by corrugated layers of PO4 and ZnO4 tetrahedra. The resulting tunnel structure is filled by Ba2+ ions. The short distance of the V4+ center to the apical oxygen atom of the square VO5 pyramids is a typical feature of vanadyl groups.
Synthese und Kristallstruktur von Hexa(tert-butyl)bismocenium-tetrachloroaluminat / Synthesis and Crystal Structure of Hexa(tert-butyl)bismocenium Tetrachloroaluminate
Authors: Sitzmann Helmut , Wolmershäuser Gotthelf
Published: February 2015

On chloride abstraction from chloro-bis{1,2,4-tri(tert-butyl)cyclopentadienyl}bismut(III) (2 ) with aluminum trichloride the salt [{C5H2(CMe3)3
-1,2,4}2Bi]+ AlCl4
- (1) has been obtained in good yield. The crystal structure of 1 shows a bismocenium cation with nearly parallel η5 - cyclopentadienyl rings (10.2° inclination of the best planes) and only a slight bending of the Cpcent -Bi-Cpcent axis (172.9°).
Pressure Dependence of the Electrode Potentials of Some Iron(III/II), Cobalt(III/II), and Ni(III/II) Couples in Aqueous Solution: Estimation of the Reaction Volumes for M(III)/M(II) Couples
Authors: Matsumoto Mitsuru , Tarumi Toshiyasu , Takahashi Isao , Funahashi Shigenobu , Noda Toshiaki , Takagi Hideo D.
Published: February 2015

Pressure dependence of the electrode potentials for various M 3+/2+ couples (M = Fe, Co, and Ni with o-phenanthroline, bipyridine, terpyridine, 1,4,7-triazacyclononane, and 1,4,7-tri-thiacyclononane) was measured by cyclic voltammetry in aqueous solution vs. a Ag/AgCl reference electrode. The reaction volume of the Ag/AgCl reference electrode was estimated from the change in the partial molar volumes of Feaq
3+/2+ and Co(terpyridine)2
3+/2+ couples, and the volumes for the formation of M2+ from M3+ were determined. The electrostrictive component for the change in the oxidation state for the M3+/2+ couple was calculated on the basis of the Drude-Nernst equation and by the mean spherical approximation (MSA). The isolated volumes for the formation of M2+ from M3+ were compared with the values predicted by theory.
Komplexbildung und Ligandeneigenschaften der Chlormethylchlorphosphane R(Cl)P-CH2-Cl - Molekülstruktur von trans-Cl2Pd[tBu(Cl)P-CH2-Cl]2 / Coordination Chemistry and Ligand Properties of Chloromethylchlorophosphines R(Cl)P-CH2 -Cl - Molecular Structure of trans-Cl2Pd[tBu(Cl)P-CH2 -Cl]2
Authors: Machnitzki Peter , Stelzer Othmar , Landgrafe Claudia
Published: February 2015

Reaction of the chloromethylchlorophosphines R(Cl)P-CH2-Cl (R = Cl, tBu, C6H11, NEt2, NPh2) (L) with C7H8Mo(CO)4 or (CO)5W(Py), (CO)6W and (CO5W(THF) yields the complexes cis-Mo(CO)4L2(2a - 2e) or (CO)5 WL (3a - 3c), respectively, in high yields. The palladium(II) complexes PdCl2L2 (4a - 4c) are obtained on treatment of 1a, 1b and 1e with 1,5-cyclooctadiene palladium(II) chloride or anhydrous palladium(II) chloride in a homogeneous or heterogeneous reaction, respectively. 4a - 4c are formed as a mixture of cis- and trans-isomers. The 13C {1H} NMR and 1H NMR spectra of 2a - 4c have been analysed, the trans-structure of 4c could be assigned to the predominant isomer. The X-ray structural analysis of 4c (triclinic, space group Pl̅) reveals a trans-square planar coordination at palladium with an antiperiplanar arrangement of the bulky tBu substituents at the phosphorus atoms. Electronic (ƩXi
Mo) and steric ligand parameters (θ) are given for the chloromethylchlorophosphines R(Cl)P-CH2-Cl (R = Cl, tBu, C6H11, NEt2, NPh2).
Wechselwirkungen in Molekülkristallen, 127 [1] Die unterschiedlichen Strukturen des im Kristall verdrillten 1,4-Bis(tricyanvinyl)- benzols sowie des eingeebneten 1-Tricyanvinylbenzols, Dichtefunktional- Berechnungen und cyclovoltammetrisch sowie ESR/ENDOR-spektroskopisch charakterisiertes Reduktionsverhalten / Interactions in Molecular Crystals, 127 [1]The Different Structures in the Crystal of Twisted 1,4-Bis(tricyanovinyl)benzene as well as of Planar 1-Tricyanovinyl-benzene, Density Functional Calculations and Reduction Behaviour Studied by Cyclovoltammetry and ESR/ENDOR Spectroscopy
Authors: Bock Hans , Seitz Wolfgang , Nagel Norbert , Baur Rüdiger , Bats Jan W. , Havlas Zdenek , Claridge Rodney F. C.
Published: February 2015

The attempted crystal growth of 1,4-bis(tricyanovinyl)benzene dianion salts, although without success so far, has provided information of general interest. The crystal structures of the related mono and 1,4-bis(tricyanovinyl)benzene derivatives differ considerably in their substituent group twisting angles: The two tricyanovinylbenzenes in split-positions exhibit dihedral angles of only 6° or 11°, whereas the two C2(CN)3 groups of the disubstituted benzene are conrotationally twisted by 48° out of the benzene plane. Density functional calculations with 6 - 311++G** basis sets, however, predict identical values of 32° for both compounds and, therefore, their crystal arrangements are discussed in detail for packingenforced additional interactions. Cyclovoltammetric and ESR/ENDOR-measurements provide information on the redox behaviour, a prerequisite for attempts to crystallize molecular anion salts: The 1,4-disubstituted derivative with a cyclovoltammetrically determined halfwave reduction potential of +.14 V in aprotic THF solution proves to be one of the strongest polycyano-substituted π-acceptors and its radical anion can be selectively generated by T1 metal reduction as confirmed by its ESR/ENDOR spectra.
Synthesis, Spectroscopy and Structure of Diorganotin(IV) Schiff Base Complexes
Authors: Dey Dilip Kumar , Das Mrinal Kanti , Nöth Heinrich
Published: February 2015

Three diorganotin(IV) chelates with a tetradentate Schiff base, H2Vanophen, [H2Vanophen = N,N′-1,2-phenylen-bis(3-methoxysalicylideneimine)] of the type R2Sn(Vanophen) (R = Ph: 1; R = n-Bu: 2; R = Me: 3) have been synthesized by the reaction of R2SnCl2 (R = Ph, n-Bu, Me) and H2 Vanophen in the presence of triethylamine in benzene. The complexes have been characterised by IR and NMR spectroscopy and by elemental analysis. The δ(119Sn) values for the complexes 1 - 3 are -543.0, -414.2 and -398.2 ppm respectively, indicating hexacoordinated Sn centers. These have been ascertained by X-ray crystal structure determinations of 1 and 3. The distances between tin and the two axial carbon atoms in each complex differ not significantly [2.17(1) Å in 1, and 2.100(3) and 2.115(3) Å in 3). The C-Sn-C angles for 1 and 3 are 165.9(4)° and 159.96(9)°, respectively. The solution NMR spectra (1H , 13C, 119Sn) show clearly that the solid state structures are retained in solution.
Synthese und Aggregatbildung eines 5-Hydroxy-2,5-dihydropyrrols. Enantiomerenreine, eindimensionale Stränge durch Wasserstoffbrückenbindungen und chiroselektive Selbstorganisation/Synthesis and Aggregation of a 5-H ydroxy-2,5-dihydropyrrole. Enantiomerically Pure, One-dimensional Strands via Hydrogen Bonds and Chiroselective Self Organization
Authors: Saalfrank Rolf W. , Nachtrab Jochen , Reck Stephan
Published: February 2015

Reaction of dimethyl 1,3-acetonedicarboxylate 8 with oxalylchloride 2 and magnesium chloride as catalyst yielded 2,3-dioxo-2,3-dihydrofuran 9, which is in equilibrium with tautomer 10 (9:10 = 1:2). Addition of thionyl chloride to a mixture of 9/10 afforded 3-chloro-2(5H)-furanone 11. The structure of 11 was unequivocally established by X-ray diffraction, which indirectly proved the structure of 10 as well. Ring opening of 11 by nucleophilic attack with benzylamine 14 in C2-position and subsequent recyclization led to racemic 3-chloro-5-hydroxy-2-oxo-2,5-dihydropyrrole 15. According to a single crystal X-ray analysis, 15 aggregates via stereospecific self selection through hydrogen bonds to give chiroselectively the one-dimensional strands ∞
1[(S)-15] and ∞
1[( R)-15]
Cyclisierungen über Enamin-Zwischenstufen bei Amindehydrierungen/Cyclizations via Enamine Intermediates with Amine Dehydrogenations
Authors: Möhrle H. , Mehrens J.
Published: February 2015

The mercury-edta dehydrogenation of the 4′-aminosubstituted-acetophenones 1, 8a and 9a produced the ring cleavaged derivatives 7 ,11a and 12a, while the piperidine and its derivatives 10a - 10e gave rise to tetracyclic compounds 16a - 16e and to methylenedi-enamines 19a - 19d, the additionally C-1-fragment in 19a - 19d probably coming from mercury edta. With addition of m-nitrobenzaldehyde to the mercury-edta dehydrogenation of substituted phenylpiperidines another route only generated the di-enamines 22.
Synthese und Reaktionsverhalten von Stannyloligosilanen, I. Kettenförmige Stannyloligosilane mit SiMe2-Einheiten/Synthesis and Reactivity of Stannyloligosilanes, I. Stannyloligosilane Chains Containing SiMe2 Moieties
Authors: Uhlig Frank , Kayser Christian , Klassen Ralph , Hermann Uwe , Brecker Lothar , Schürmann Markus , Ruhland-Senge Karin , Englich Ulrich
Published: February 2015

Stannyloligosilanes 1 and 2 with terminal organotin groups are available by reacting alkali metal tri- or diorganostannides with α,ω-dichloro- or difluorosilanes, or by treatment of organochlorostannanes with α,ω-difluorosilanes in the presence of magnesium . Attempts to functionalize the triorganotin derivatives 2 by halogenation reagents did not result in the halogen compounds 5; instead cleavage of silicon-tin bonds is observed. In contrast, reactions of the hydridotin derivatives 1 with CHX3 (X = Cl, Br) lead to the quantitative formation of the bis(chloro- or bromostannyl)oligosilanes 5. A ll compounds were characterized by NMR, IR, MS and elemental analysis. In addition, the triorganotin compound 2i and the hydridotin species 1b have been characterized by X-ray crystallography.
Die Kristallstrukturen von Tetraphenylphosphonium- octahalogenodiarsenat( III) und -diantimonat(III) mit Acetonitril, (PPh4)2[E2X8] · CH3CN (E = As, Sb; X = CI, Br)/The Crystal Structures of Tetraphenylphosphonium Octahalogenodiarsenate (III) and Diantimonate (III) with Acetonitrile, (PPh4)2[E2X8]·CH3CN(E=As, Sb; X=Cl, Br)
Authors: Czado Wolfgang , Rabe Susanne , Müller Ulrich
Published: February 2015

(PPh4)2[As2Cl8] · CH3CN was obtained from PPh4Cl and S2Cl2 with As or As4S4 or AsCl3 in acetonitrile. PPh4Cl, S2Cl2 and Sb2S3 yielded (PPh4)[Sb2Cl8] CH3CN. PPh4Br and AsBr3 gave (PPh4)2[Sb2Br8]-CH3CN. AsCl2OPh (from AsCl3 and NaOPh) reacted with Ph4Br in acetonitrile in the presence of Na2Se, selenium, and HCl, affording (PPh4)2[As2Br4,2Cl3,8] · CH3CN. According to their X-ray crystal structure determinations, all products are isotypic (space group C2/c, Z=4). The centrosymmetric anions consist of two ψ octahedra sharing an edge. In the [As2Br4,2Cl3,8]2- ion the bridging positions are taken solely by bromine atoms, whereas Br and Cl atoms occupy the other halogen positions randomly.
Tris(ethyldimethylphenylammonium) nonahalogenodibismuthates(III)
Authors: Eickmeier H. , Jaschinski Bernd , Hepp A. , Nuß Jürgen , Reuter Hans , Blachnik Roger
Published: February 2015

The halogenobismuthates Q3Bi2X9 (Q = EtMe2PhN; X = Cl, Br, I) were prepared by reaction of BiX3 with EtMe2PhNX in ethanol. Single crystal structure determinations yielded: [EtMe2PhN]3[Bi2Cl9], S.G. P212121, Nr. 19, a = 952.5(3), b = 1184.1(4), c = 3726.4(9 pm, Z = 2;[EtMe2PhN]3[Bi2Br9] S.G .P21/c , No. 14, a= 1839.4(4),b= 1329.5(3), c = 1817.3(6)pm, β = 92.68(3)°, Z = 4, [EtMe2PhN]3[Bi2l9], ], S.G . P21/c, No. 14, a = 1915.3(2), b = 1379.0(3), c = 1890.9(5) pm, β = 92.48(1)°, Z = 4. The thermal behaviour was investigated with the aid of DSC measurements and temperature dependent X-ray powder diffraction. All compounds undergo a transition into a high temperature modification which could be obtained in case of [EtMe2PhN]3[Bi2Br9-xIx] in form of single crystals: S.G . P21/c, Nr. 14, a = 1002.7(5), b = 1278.7 (8), c = 3584.3(5) pm, β = 90.12(2)°, Z = 4. Surprisingly in this compound the iodine atoms are not statistically distributed over all possible bromine positions, but occupy only one position. Lattice parameters of the other high temperature modifications and enthalpies of transition of the compounds are given. In addition a second iodobismuthate was isolated:[EtMe2PhN]4[Bi6l22], S.G . P1̄, Nr. 2 , with lattice parameters of a = 1343.4(3), b = 1554.3(3), c = 2262.5(6) pm, a = 100.89(3)°, β = 96.63(1)°, 7 = 98.94(2)° and Z = 2.
Komplexe zweier vierzehngliedriger Tetraazadibenzo-Makrocyclen. Strukturen eines freien Liganden und von Nickel(II)-, Kupfer(II)- und Zink(II)-Komplexen / Complexes of Two 14-Membered N4 Dibenzo Macrocycles. Crystal Structures of a Free Ligand and of Nickel(II), Copper(II) and Zinc(II) Complexes
Authors: Mattes Rainer , Voet Ulrich
Published: February 2015

The syntheses and structural characterizations of complexes of two 14-membered macrocyclic trans-N4 dibenzo ligands, 5,7,8,9,14,16,17,18-octahydrodibenzo[e,1]-[1,4,8,11-tetraazacyclotetradecine- 6,15-dimethyl (L3) resp. -6,15-diacetamide (L4), are presented. The crystal structures of five compounds have been determined by single crystal X-ray diffraction. The free ligand L3 has a saddle-shaped structure with intramolecular hydrogen bonds. This conformation of the ligand exists also in the Zn(II) complex in which the metal ion is five-coordinated with the metal center outside the cavity. The coordination polyhedron is intermediate between a trigonal bipyramid and a square pyramid. In cis-[Ni(L3)(NCS)2] the ligand is folded along an N ⋯ N axis. The nickel ion in this complex shows an approximate octahedral geometry. For Ni(II) and Cu(II) complexes of ligand L the overall geometry is also distorted octahedral. The folding of the ligand causes a cis-N4O2 coordination.
Metallkomplexe mit 2,2'-Dipyridylamin als Liganden: Kristallstrukturen der Komplexe mit CdX2 (X = Cl, Br, I) und CuCN / Metal Complexes with 2,2'-Dipyridylamine as Ligand: Crystal Structures of the Complexes with CdX2 (X = Cl, Br, I) and CuCN
Authors: Pickardt Joachim , Staub Benedikt
Published: February 2015

Reactions of 2,2′-dipyridylamine (dpyam) with cadmium halides yield crystals of [Cd(dpyam)(H2O )Cl2] (1), [Cd(dpyam)Br2] (2), and [Cd(dpyam)I2] (3). With CuCl2 and KCN a complex [Cu(dpyam )CN] · H2O (4) is obtained. Depending on the size of the halide ions the coordination changes from octahedral in 1 to trigonal bipyramidal in 2 and tetrahedral in 3. The coordination in 4 is trigonal. Due to the geometric strain imposed by the ligand all coordination polyhedra show significant distortions. 1 and 2 form dimers by halide bridges. With the exception of 3 all compounds form “supramolecular” structures via hydrogen bonds, e.g. chains or networks.
Kristallstruktur von Hydrogenoxonium-Hexachloroantimonat-Bisacetonitril / Crystal Structure of Hydrogenoxonium Hexachloroantimonate-Bisacetonitrile
Authors: Minkwitz Rolf , Hirsch Claudia
Published: February 2015

The formation of hydrogen bonds to acetonitrile molecules lends stability to the hitherto unknown hydrogenoxonium hexachloroantimonate H3O+SbCl6
- . The structure of H3O+SbCl6
- · 2 CH3CN was determined on a single crystal. It crystallises in the orthorhombic space group Pmn2( 1) (Nr. 31) with Z = 2, a = 1 12,7( 1 ),b = 988,8( 1) and c = 1036,5( 1) pm.
Synthese von muscarinanalogen Epoxiden aus Campholenund Fencholenverbindungen / Synthesis of Muscarin Analogue Epoxides from Campholenic and Fencholenic Compounds
Authors: Anhalt Katrin , Schulze Klaus , Jörchel Peter , Gavranic Marijana
Published: February 2015

In connection with the synthesis and epoxidation of campholenic and fencholenic derivatives some trimethylammonium iodides (2 and 4) similar to muscarin were prepared. They may be of interest for the investigation of the cholinergic receptor. The stereochemistry of the epoxytrimethylammonium iodide 4a was determined by NMR and X-ray analysis.
Alquds, a New Flavone Glycoside from Calamintha incana
Authors: Dardass Abdul-Khaliq , Firdous Sadiqa , Ali Zulfiqar , Ahmad Viqar Uddin
Published: February 2015

Alquds, a new flavone glycoside was isolated from the aerial parts of Calamintha incana and identified on the basis of spectral data (1- and 2-D NMR, IR, UV ) and comparative study.
1.3.5-Triazin-2,4,6-trisulfenyltrichlorid: Synthese, Eigenschaften und Reaktionsverhalten / 1.3.5-Triazine-2,4,6-trisulfenyltrichloride: Synthesis, Properties and Reactions
Authors: Tripolt Robert , Schmuck Siegfried , Nachbaur Edgar
Published: February 2015

Various routes and improved experimental conditions for the synthesis of 1,3,5-triazine-2,4,6- trisulfenyltrichloride are reported and its reaction with water, alcohols, ammonia, and acetone investigated. The formation of the monomeric pseudohalogen halide NCS-C1 by degradation of the title compound under mass-spectrometry conditions has been observed.
Kristallstruktur des „supramolekularen“ Komplexes [K(Benzo-18-krone-6)][Zn(CN)3]*H2O mit einem polymeren kettenförmigen Tricyanozincat-Anion / Crystal Structure of the “Supramolecular” Complex [K(benzo-18-crown-6)][Zn(CN)3] •H2O with a Polymeric Tricyano Zincate Anion with Chain Structure
Authors: Pickardt Joachim , Wischlinski Pirka
Published: February 2015

Crystals o f the complex [K (benzo-18-crown-6][Zn(CN)3] H2O were obtained from a solution o f Zn(CN)2, KCN, and benzo-18-crown-6 in water/methanol. The compound crystallizes in the triclinic space group PI (no. 2),: Z = 2, a = 818,6(5), b = 1236,7(8), c = 1359,6(6) pm, a = 67,02(4), β = 87,38(4), 7 = 75,46(5). Each Zn atom is bonded to one bridging cyanide ion to give chains -Zn(CN)Zn -, and to two terminal CN groups. The N atom of one of the terminal CN groups interacts with a potassium ion o f the [K (benzo-18-crown-6)]+ unit. The coordination spheres of the K ions are completed by water molecules, which in turn form hydrogen bonds to N atoms of terminal CN groups of neighbouring chains, whereby puckered sheets are formed
Synthese und Röntgenstrukturanalyse der ersten terf-Butylcalix[4]arensalze mit einem Phosphonium-Kation / Synthesis and X-Ray Structure Analysis of the First rm-Butylcalix[4]arene Salts with a Phosphonium Cation
Authors: Siedentop Tjark , Neda Ion , Thönnessen Holger , Jones Peter G. , Schmutzler Reinhard
Published: February 2015

The reactions o f ter/-butylcalix[4]arene (1) and the phosphorus-substituted rm -butylcalix- [4]arene (2), respectively, with terf-butylbis[N-(N',N',N",N"-tetramethyl)guanidinyl]phosphine (3) led to the first calix[4]arene-anions with the protonated phosphonium cations 4 and 5. No protonation o f the imino nitrogen atom was observed. In the case of compound 4, a singlecrystal X-ray structure analysis has been conducted. In compound 5, phosphorus atoms in the oxidation states +III and +V are present in one molecule
Zatatriol: A New Aromatic Constituent from Zataria multiflora
Authors: Ali Muhammad Shaiq , Saleem Muhammad , Ahmad Viqar Uddin
Published: February 2015

A new isopropyl benzene derivative named as zatatriol (5) and two synthetically known compounds (2 and 7) having the same skeleton have been isolated from the hexane soluble part of a Lamiaceous plant Zataria multiflora. In addition to 2, 5 and 7, some known constituents: p-cymene (1), thymol (3), thymol methyl-ether (4) , /3-sitosterol, stigmasterol, oleanolic acid, betulinic acid, and hexadecanoic acid have also been isolated from the same source. Structures of the isolated constituents were elucidated with the aid of NM R spectroscopy
Die Kristallstruktur von [(THF)LiCl]n / The Crystal Structure of [(THF)LiCl]n
Authors: Kopp Mike R. , Neumüller Bernhard
Published: February 2015

Single crystals of [(THF)LiCl]n (1) were obtained by the reaction of (PhCH2)2GaCl with LiSe'Bu in THF/toluene. 1 is polymeric in the solid state and crystallizes in the space group Pbcn, Z = 8, lattice dimensions at -83 °C; a = 1438.6(2), b = 1140.9(2), c = 746.2(1) pm, R1 = 0.0395
Reaktionen von Isochinolinium-Salzen mit Hydroxylamin-Derivaten, 3. Mitteilung. Mechanismus der Aminoxid-Bildung / Reactions of Isoquinolinium Salts with Hydroxylamine Derivatives, 3rd Communication. Mechanism of Amine Oxide Generation
Authors: Möhrle H. , Nießen R.
Published: February 2015

2-Methylpapaverinium iodide (1) reacted with hydroxylamine to papaverine-N-oxide (2), but without a detectable intermediate and only in moderate yield, caused by the steric hindrance of the 1-substituent. The ring opened product of 2-dinitrophenylisoquinolinium salt with hydroxylamine, the enamine-oxime 3b gave rise to a 3-substituted cyclic nitrone (6), when heated with triethylamine. This alkali-stable compound was transformed with acid quantitatively to isoquinoline-N-oxide (4). The enaminonitrile 9c, treated with triethylamine showed cyclization to the iminoisoquinoline 10, which by loss of nitrous acid produced the tetracyclic azaindole 11. The 2-methoxyisoquinolinium salt 16 was cleaved with O-methylhydroxylamine to the resistant di(O-methyloximes) (20a/b), unable to form the amine oxide 4. From these and former results, a mechanism for the ring opening of cycliminium salts and the recyclization to amine oxides was proposed.
Bis-phosphonio-isophosphindolide Copper Complexes
Authors: Gudat Dietrich , Holderberg Andreas W. , Korber Nikolaus , Nieger Martin , Schrott Martin
Published: February 2015

Bis-triphenylphosphonio-isophosphindolide salts 1[X] react with Cu(I)-halides CuX to give isolable products of composition [(1)Cu2X3 ]. X-ray crystal structure analyses confirmed that for X = Br, Cl dinuclear complexes [(μ-1 )(μ-X)Cu2X2] with μ2, η1(P)-bridging cations 1 are formed, while for X = I a solid phase containing a salt (1)2[Cu4I6] and a complex [(1)2Cu4I6] with a terminal η1(P)-coordinated ligand 1 was obtained. The bonding parameters in the two types of complexes suggest that l i s a hybrid between a phosphenium cation and a phospholide anion whose π-system is less nucleophilic than the phosphorus lone-pair.31P NMR studies revealed that in solution in all cases binuclear complexes [(1)Cu2X3] are in dynamic equilibrium with small amounts of mononuclear species and free 1. The same equilibria were detected in the system 1[OTf]/CuOTf. NMR studies of ligand exchange reactions indicated that the stability of complexes [(1)Cu2X3 ] increases in the order X = OTf < I < Br, Cl, and titration of [(1)Cu2Br3] with Et4NBr allowed to determine the equilibrium constant of the complex formation reaction.
Interaction between the Peroxide Adduct of Binuclear Iron(III) Complex with (HPTP) Anion and the Sugar Moiety of Nucleosides
Authors: Nishino Satoshi , Kunita Mami , Kobayashi Teruyuki , Matsushima Hideaki , Tokii Tadashi , Nishida Yuzo
Published: February 2015

We have in this study obtained the experimental evidence to suggest that the peroxide adduct of binuclear iron(III) complex with H(HPTP) directly reacts with the sugar moiety of the DNA chain, to cleave it; H(HPTP) denotes N,N,N′,N′-tetrakis(2-pyridylmethyl)-1,3-diamino- 2 -propanol.
Thermische Zersetzung und Lösungskalorimetrie von Ammoniumneodymbromiden / Thermal Decomposition and Solution Calorimetry of Ammonium Neodymium Bromides
Authors: Hennig C. , Oppermann H.
Published: February 2015

The thermal decomposition equilibria of ammonium neodymium bromides (NH4)3NdBr6, (NH4)2NdBr5 and NH4Nd2Br7 have been investigated by total pressure measurements. The thermodynamical data of these solid phase complexes have been derived from the decomposition functions. The standard enthalpies of solution in 4N HBr (aq.) of (NH4)3NdBr6, (NH4)2NdBr5, NH4Nd2Br7, NdBr3 and Nd2O3 were measured. On the basis of these values and tabulated data, the standard enthalpies at 298 K of the ammonium neodymium bromides were derived and compared with the results obtained from the total pressure measurements.

Data by total pressure measurement: ΔH°B((NH4)3 NdBr6,f,298) = -399,1 ± 4,9 kcal/mol; S°((NH4)3NdBr6,f,298) = 153,4 ± 7,4 cal/K.mol; ΔH°B((NH4)2NdBr5,f,298) = -343,0 ± 4,4 kcal/mol; S°((NH4)2,NdBr5,f,298) = 109,9 ± 6,8 cal/K.mol; ΔH°B(NH4Nd2Br7,f,298) = -484,0 ± 5,1 kcal/mol; S°(NH4Nd2Br7,f,298) = 127,9 ± 6,6 cal/K.mol.

Data by solution calorimetry: ΔH°B(NdBr3,f,298) = -208,7 ± 1,6 kcal/mol; ΔH°B((NH4)3- NdBr6,f,298) = -404,8 ± 2,7 kcal/mol; ΔH°B((NH4)2NdBr5,f,298) = -344,2 ± 2,4 kcal/mol; ΔH°B(NH4Nd2Br7,f,298) = -482,7 ± 3,7 kcal/mol.
Novel Dinucleating Ligand Systems Containing Two Adjacent Coordination Compartments of the Potential Triamidoamine-Type - Nickel(II) and Cobalt(II) Coordination Chemistry
Authors: Buchler Silke , Meyer Franc , Jacobi Albrecht , Kircher Peter , Zsolnai Laszlo
Published: February 2015

The preparation of novel dinucleating pyrazolate ligands H5L3 - H5L8 carrying chelating side arms with appending secondary amine functions is reported. Following different synthetic routes, either CH2CF3, C6H2F3 , or C6F5 moieties can be introduced as substituents at the terminal nitrogen atoms. These systems are reminiscent of two coupled coordination compartments of the potential triamidoamine-type. Crystallographic analyses of a series of bimetallic complexes of the CH2CF3 -substituted ligand H5L4 with NiCl2 and CoCI2 reveal manifold coordination modes in the solid state, resulting from the facile detachment of a single or several N-donor sites from the metal centers. Coordination number sets {4/6} (in H5L4Co2Cl4) and {5/6} (in H4L4Ni2Cl3, H4L4Co2 Cl3 and H5L4Ni2Cl4) are thus observed. In the non-deprotonated H5L-type systems the remaining protons are found to be scavenged by a pyrazolate-N (in H5L4Ni2Cl4) or an amine function of a ligand side arm (in H5L4Co2Cl4).
An Approach to the Synthesis of New 1-Phenylacridones and Naphthacridones
Authors: Thamaraiselvi S. , Mohan P. S.
Published: February 2015

A short synthesis of 1-phenylacridones, Napth[2,1-a]acridones and Napth[2,3-a]acridones is described, starting from 4-hydroxy-2-methylquinoline by condensing it with respective aldehydes followed by oxidative photolytic cyclization.
Darstellung und Kristallstruktur von Lithiumozonid-Ammoniakat (1/5) LiO3 · 5 NH3/Synthesis and Crystal Structure of Lithiumozonide-Ammonia (1/5) LiO3 · 5 NH3
Authors: Klein Wilhelm , Jansen Martin
Published: February 2015

Lithium ozonide has been synthezised starting from cesium ozonide via cation exchange in liquid ammonia and crystallizes at -78°C as an ammoniate, LiO3 · 5NH3. The coarse, ruby red crystals decompose above the boiling temperature of ammonia and are extremely sensitive to moisture. The crystal structure of L iO3 · 5NH3 (P c21n; a = 1231.9(5), b = 637.4(2), c = 1104.8(4) pm; Z = 4; R1 = 4.57%; 1318 independent reflections) consists of lithium tetramine complexes, ozonide anions and non coordinating ammonia molecules. With respect to the arrangement of the complex cations and of the anions there is similarity to the WC type of structure. The central oxygen atom of the ozonide anion is disordered.
N,N′-Bis(trimethylsilyl) benzamidinato-Komplexe von Vanadium(V), Niob(V) und Tantal(V)/ N,N′-Bis(trimethylsilyl)benzamidinato Complexes of Vanadium(V), Niobium(V) and Tantalum(V)
Authors: Preuss Fritz , Scherer Michael , Klingshirn Christoph , Hornung Gabriele , Vogel Monika , Frank Walter , Reiß Guido
Published: February 2015

N,N′-Bis(trimethylsilyl)benzamidinato complexes of vanadium(V), niobium(V) and tantalum( V) have been prepared starting from tBuN=MCl3 · n py and tBuN=MCpCl2, respectively: tBuN=V[PhC(NSiMe3)2] nCl3-n (n = 1, 2); tBuN=M[RC(NSiMe3)2]Cl · py [M = Nb. Ta; R = C6H5, C6H4(4-CF3)]; tBuN=MCp[RC(NSiMe3)2]Cl [M = V. Nb, Ta; R = C6H5, C6H4- (4-CF3)]; tBuN=VCp[PhC(NSiMe3)2](OtBu). The syntheses of silylated tert-butylamido complexes tBuN=M[NtBu-SiMe2-NHtBu]Cl2 · py (M = Nb, Ta), tBuN=V[NtBu-SiMe2-OtBu]Cl2 and tBuN=M[NtBu-SiMe2-OtBu]Cl2 · py [M = Nb, Ta (20)] are also described. The compounds have been investigated by 1H NMR data,51V NMR data, mass spectra. X-ray data diffraction analysis.
Bis[(2-diphenyIphosphino)phenyl]phenylphosphine as an Inflexible Tridentate Ligand for Indium Trichloride
Authors: Sigl Marcus , Schier Annette , Schmidbaur Hubert
Published: February 2015

Anhydrous indium trichloride reacts with [2-(Ph2P)C6H4]2PPh (TP) in the molar ratio 2:1 to give an ionic complex [(TP)InCl2]+ InCL4
- in almost quantitative yield. The structure of the product has been determined by a single crystal X-ray diffraction study. In the cation the TP molecule acts only as a bidentate ligand via its two terminal phosphorus atoms [In-P1 2.5956(8), In-P2 2.5799(7) Å], Although the central phosphorus atom is also rather close to the metal atom [2.8259(8) Å], the In-P3 interaction is inefficient because of an adverse orientation of the lone pair of electrons at P3 owing to the steric inflexibility of the ligand. Accordingly, the 31P NMR spectra of the compound in CD2CI2 show large contact shifts and quadrupole broadening only for the signals of the two terminal phosphorus atoms, whereas the lines of the central phosphorus atom are less shifted and well resolved (AB2 spin system at -60°C).
Preparation and Crystal Structure of the Calcium Rhenate(VI, VII) Ca5Re3O15-x
Authors: Jeitschko Wolfgang , Mons Horst A. , Rodewald Ute Ch.
Published: February 2015

The title compound was prepared by reaction of elemental calcium with the calcium metaperrhenate Ca(ReO4)2. Its crystal structure was determined from single-crystal X-ray data: Amm2, a = 560.31 (5)pm, b = 1572.4( 1)pm, c = 719.91 (6)pm ,Z = 2 ,R = 0.033 for 930 structure factors and 46 variable parameters. The calcium atoms occupy three atomic sites, all with seven oxygen neighbors. Of the two different rhenium atoms one has square-pyramidal oxygen coordination with an average oxidation number +6.25. The other rhenium site (oxidation number +7) was refined as a split position with trigonal-bipyramidal (75%) and tetrahedral oxygen coordination (25%). One oxygen site remains unoccupied, whenever the tetrahedral rhenium site is occupied, resulting in the composition Ca5Re3O14.75. A test for superconductivity of this black compound down to 1.5 K was negative.
A Simple and Convenient Route to Arylxenon(II) Tetrafluoroborates
Authors: Frohn H.-J. , Franke H. , Bardin V. V.
Published: February 2015

An improved synthesis of arylxenon(II) salts is reported. The series of fluoro-containing arylxenon(II) tetrafluoroborates (aryl = C6F5, 2,3,4,5-C6HF4, 3,4,5-C6H2F3 and 3,5-C6H3F2) are prepared by the reaction of xenon difluoride with the corresponding aryldifluoroboranes. The salts [C6F5Xe] [BF4] and [2,3,4,5-C6HF4Xe] [BF4] are long-term stable in anhydrous HF (aHF) solution at rt, while [3,4,5-C6H2F3Xe] [BF4] and [3,5-C6H3F2Xe] [BF4] are converted into 1,2,3,5-tetrafluorobenzene and 1,3,5-trifluorobenzene, respectively, within a few hours.
Three-dimensional Copper(I) Halide Based Coordination Networks with Asymmetrically Substituted Bridging N-Donor Ligands
Authors: Roßenbeck B. , Sheldrick W. S.
Published: February 2015

The discrete complex [(Cul)2 (pyzCN)4] (1) and the coordination polymers 1
∞ [CuI(pyzCN)] (2) and 3
∞ [(CuX)3 (pyzCN)2] (3, 4; X = Br, Cl) may be prepared from the respective copper(I) halide CuX and 2-cyanopyrazine (pyzCN) by self-assembly in acetonitrile solution at 100- 120°C. Whereas 2 exhibits 1 [Cul] staircase double chains as its characteristic substructure, the three-dimensional networks of 3 and 4 contain single zigzag CuX strings. The influence of the copper(I) halide on both the connectivity pattern and the dimensionality of a resulting coordination network is particularly apparent for the 1:1 complexes 1
∞ [CuI(pymMe)] (5), 3
∞ [(CuBr)3(pymMe)3] (6) and 2
∞ [CuCl(pymMe)] (7), which were generated by reaction of CuX with 4-methylpyrimidine (pymMe) under reaction conditions similar to those above.
Chinazolinderivate durch Cyclodehydrierung von N-(2-substituierten Aryl)-Piperidinen / Quinazoline Derivatives by Cyclodehydrogenation of N-(2-Substituted Aryl)-Piperidines
Authors: Möhrle H. , Jeandrée M.
Published: February 2015

Dehydrogenation of the N-[2-(aminocarbonyl)phenyl]piperidines 1 -5 using Hg(II)-EDTA, generated the quinazolinones 6 -9 . Increasing size of the 4-substituent in the piperidine decreased the oxidation rate and the product yield.

N-[2-(Hydroxyiminomethyl)phenyl]piperidines 18-22 showed a different behaviour. While 18 with H g(II)-EDTA in water produced the oxime lactam 24 in quantitative yield, the 4- substituted piperidines 19-21 caused not only a lower reaction rate but also an altered product pattern. The double dehydrogenation to lactams was reduced and the cyclic nitrones, formed by two electron withdrawal, became dominant. From the spiro compounds 21 and 22, solely the quinazoline-N-oxides 29 and 30 resulted. The mechanism of the reactions is discussed.
Reactions of Cyanothioacetamide Derivatives with 2-Hydrazinothiazol-4(5H)-one: Synthesis, Cyclization and Biological Evaluation of Several New Annelated Pyran, Thiazole, 1,2,4-Triazole and 1,2,4-Triazine Derivatives
Authors: Eldin Sanaa M.
Published: February 2015

The thiocarboxamidocinnamonitriles (2) reacted with 2-hydrazinothiazol-4(5H)-one (3) to afford the corresponding pyrano[2,3-d]thiazoles (6). Compounds 6 were used for the synthesis of several new annelated pyran, thiazole, 1,2,4-triazole and 1,2,4-triazine derivatives via their reactions with chloroacetic acid, ethyl chloroformate, diethyl oxalate and acetylacetone. Structures were established based on elemental and spectral data studies. Some of the newly synthesized heterocyclic derivatives were tested for their antimicrobial activity.
Structure of the 2-Pyrrolidinone Monohydrate
Authors: Pirilä Päivi , Mutikainen Ilpo , Pursiainen Jouni
Published: February 2015

The X-ray crystal structure of the 1:1 adduct shows a complicated network of water and 2-pyrrolidinone molecules where the carbonyl oxygen atom of 2-pyrrolidinone forms hydrogen bonds with protons of two separate water molecules and the NH proton of the 2- pyrrolidinone molecule interacts with the oxygen atom of a third water molecule.
Coordination of the Hetero(N,S)- bidentate Ligand 1-Methyl-2- (methylthiomethyl)-1H-benzimidazole to [(Ph3P)Au)]+ Exclusively through the Imine Nitrogen Donor
Authors: Albrecht Markus , Hiibler Klaus , Kaim Wolfgang
Published: February 2015

1-Methyl-2-(methylthiomethyl)-1H- benzimidazole (mmb, N^S) was reacted with Ph3PAuCl/AgPF6 in THF to yield [(Ph3P)Au(mmb)](PF6) which could be crystallographically characterized. The Au+ ion is almost linearly coordinated by the triphenylphosphine P and the imine N atom of a monodentate N^S ligand. There is no gold(I)-sulfur bonding as the distance of ca. 3.02 Å indicates. Similarly, close intermetallic contacts between the gold centers are absent. Both effects are attributed to the positive charge on the metal.
Die Kristallstrukturen von Ph3AsCI2 und β-Ph3AsBr2 / Crystal Structures of Ph3AsCI2 and β-Ph3AsBr2
Authors: Neumüller Bernhard , Chitsaz Soheila , Dehnicke Kurt
Published: February 2015

Colourless single crystals of Ph3AsCl2 as well as of β-Ph3AsBr2 were obtained from acetonitrile solutions and were suitable for X-ray structure determinations. Ph3AsCl2: Space group P212121, Z = 4, lattice dimensions at -90 °C: a = 1247.9(2), b = 1267.5(1), c = 1033.4(1) pm, R x = 0.0484.

β-Ph3AsBr2: Space group P1̄ , Z = 4, lattice dimensions at -80 °C: a = 949.1(1), b = 1189.7(1), c = 1693.7(2) pm, a = 98.32(1)°, ß = 103.64(1)°, γ = 109.44(1)°, R x - 0.0628. The structures consist of Ph3AsX2 molecules (X = Cl, Br) with trigonalbipyramidal coordination of the arsenic atom with the halogen atoms in the axial positions.
Synthesis and Structure of Chiral Silatranes Derived from Terpenes
Authors: Wagner Gabriele , Herrmann Rudolf , Pedersen BjØrn , Scherer Wolfgang
Published: February 2015

Starting with the chiral pool compounds (-)-menthone, (-)-limonene, (-)-β-pinene, and (-)-carvone, new homochiral triethanolamine derivatives were obtained and converted to chi­ral silatranes. These silatranes were characterized by crystal structure analyses and NMR techniques. Conformational analyses in the solid state and in solution show that the chiral terpene residues determine the direction of the ring puckering of the silatrane moiety.
Syntheses and Characterization of 1-Haloazagermatranes
Authors: Shutov Pavel L. , Karlov Sergey S. , Lorberth Jörg , Zaitseva Galina S.
Published: February 2015

Germanium, Azagermatranes The reaction of tris(dimethylamino)halogermanes, (Me2N)3GeHal (7, Hal = Cl; 8 , Hal = Br), with tris(2-aminoethyl)amines, N(CH2CH2NHR)3 (5, R = H; 6 , R = Me), yield l-halo-N,N',N"-azagermatranes (1, X = Cl, R = H; 2, X = Br, R = H; 3, X = Cl, R = Me; 4, X = Br, R = Me). Treatment of 4 with n-butyllithium affords l-n-butyl-N,N',N"-trimethylazagermatrane (14) in high yield. Reactions of n-BuLi with 7 or (Me2N)4Ge (13) lead to the formation of (Me2N)3Ge-n-Bu (15). On treatment of 15 with 5 the 1 -n-butylazagermatrane 16 was obtained. The molecular composition and the structures of all new compounds were established by elemental analyses, 1H and 13C NMR spectroscopy and mass spectrometry.
Synthese und Charakterisierung von cis- und trans-Dicyclohexyl-3,3′,4,4′- tetracarbonsäuren und ihren Dianhydriden / Syntheses and Characterization of cis- and trans-Dicyclohexyl-3,3′,4,4′- tetracarboxylic Acids and their Dianhydrides
Authors: Shiotani Akinori
Published: February 2015

cis- and trans-Dicyclohexyl-3,3′,4,4′-tetracarboxylic acid and their dianhydrides were prepared from tetramethyl dicyclohexyl-3,3′,4,4′-tetra-carboxylates by hydrolysis and subsequent dehydration. The trans dianhydride 2b was found to be sensitive to temperature. However, once the imide ring is formed in the reaction with an amine, the model compound is thermostable. The products were characterized by 1H and 13C NMR, and also by two-dimensional COSY spectroscopy. In the hydrolysis of cis-tetramethyl dicyclohexyl-3,3′,4,4′-tetracarboxylates in steam under high-pressure, trans-dicyclohexyl-3,3′,4,4′-tetracarboxylic acid was formed, while the treatment of cis-dicyclohexyl-3,3′,4,4′-tetracarboxylic acid in steam under high-pressure afforded also trans-dicyclohexyl-3,3′,4,4′-tetracarboxylic acid. In a deuterium tracer experiment of cis-1a, the 3,3′,4,4′-tetradeuterated dicyclohexyl-3,3′,4,4′-tetracarboxylic acid 2a was formed. An isomerization mechanism was postulated from this findings.
A One-Dimensional Polymeric Form of the Polycation Te8
2+ in the Structure of Te8[Bi4Cl14]
Authors: Beck Johannes , Stankowski Alexander
Published: February 2015

The reaction of Te, TeCl4 and BiCl3 in a sealed evacuated glass ampoule in a temperature gradient 160 to 90 °C yields Te8[Bi4Cl14] as black platelike crystals with a golden lustre which are deposited in the temperature zone 150 to 130 °C. The best yield is obtained with a Te/TeCl4/BiCl3 molar ratio of 15/3/4. The crystal structure determination (orthorhombic, P212121, a = 879.9(3), b = 1642.3(4), c = 2267.3(8) pm, Z = 4) shows that Te8[Bi4Cl14] consists of a novel one-dimensional (Te8
2+)„ polycation and a two-dimensional chlorobismutate anion Bi4Cl14
2-. The structure of the cation consists of boat shaped Te6 rings which are connected in the 1,4-positions by Te2 groups to a one-dimensional polymeric strand. The structure is substantially different from the previously reported Te8
2+ polycations in Te8[WCl6]2 and Te8[MCl6] (M = Zr, Hf, Re) where discrete bicyclic clusters with only weak interionic interactions are present. The Bi4Cl14
2- ion can be described as built up of BiCl3 molecules which are connected by Cl- ions to a two-dimensional network [(BiCl3)4(Cl-)2]n.
Kristall- und elektronische Struktur von LaAlSi2 / Crystal and Electronic Structure of LaAlSi2
Authors: Kranenberg Christian , Johrendt Dirk , Mewis Albrecht , Kockelmann Winfried
Published: February 2015

LaAlSi2 (a = 4.196(2), c = 11.437(7) Å; P3̄ml; Z = 2) was synthesized by arc-melting of preheated mixtures of the elements. The compound was investigated by means of X-ray methods and by neutron diffraction. The crystal structure can be described as a stacking variant of two different segments. The first one corresponds to the CaAl2Si2 structure type (LaAl2Si2), the second one with the A1B2 structure type (LaSi2). The segments are stacked along [001]. The electronic structure of the compound is discussed on the basis of LMTO band structure calculations.
Synthesis and Structure of Di- and Triferriostibonium Salts of the Type [Fp2SbPh2]2FeX4 and [Fp3SbR]2FeX4 (Fp = CpFe(CO)2, R = Ph, Cl; X = Cl, Br, I)
Authors: Lorenz Ingo-Peter , Schneider Rudolf , Nöth Heinrich , Polborn Kurt , Breunig Joachim
Published: February 2015

The reaction of Ph2SbSiMe3 with CpFe(CO)2X (X = Cl, Br) leads to the formation of the diphenyldiferriostibonium salts [{CpFe(CO)2}2SbPh2]2FeX4, whereas PhSb(SiMe3)2 and CpFe(CO)2Cl react to give the phenyltriferriostibonium salt [{CpFe(CO)2}3Sb]2FeCl4. Sb(SiMe3)3 reacts with CpFe(CO)2X (X = Cl, Br) to yield the halogenotriferriostibonium salts [{CpFe(CO)2}3SbX]2FeX4. The chloro derivative can also be obtained: from SbCl3 with {CpFe(CO)2}2 or Na[CpFe(CO)2], and from SbCl5 and Na[CpFe(CO)2], The compounds have been characterized by spectroscopic (IR, NMR, MS), analytical (C, H) and X-ray diffraction investigations ([{CpFe(CO)2}2SbPh2]2FeBr4, [{CpFe(CO)2}3SbPh]2FeCl4, [{CpFe(CO)2}3SbCl]2FeCl4).
Synthesis Of A Large Water-Soluble Gold Cluster (Au32.36) And Its Properties As A Potential Label In Electron Microscopy
Authors: Jahn Wemer
Published: February 2015

A water-soluble gold cluster with a core of 32 to 36 gold atoms was prepared by NaBH4 reduction of the AuCN complex of n-butyl-bis (5-morpholinocarbonyl-2-furyl)-phosphine and characterized by its mass spectrum. The chromatographic behavior, ligand exchange and binding to actin were studied
Koordination Des Anions Von 2,4-Dicyanoglutaconsäurediethylester An Tripodeisen(Ii)-Einheiten. Die Entstehung Helikaler Strukturen
Authors: Jacob Volker , Huttner Gottfried , Kaifer Elisabeth , Kircher Peter
Published: February 2015

The anion of 2,4-dicyano glutaconic acid diethyl ester, [NCC(COOEt)CHC(COOEt)CN]- (1- ), as an α,μ;-dinitrile with a three atom spacer is a highly variable ligand capable of binding in a monodentate η1-fashion, in a bidentate chelate fashion, and as a μ2-bridging entity. TripodFe(1)2, 2, [tripod = CH3C(CH2PPh2)3] contains one chelating ligand 1- and one terminally coordinated ligand 1-- . Variable temperature NMR spectroscopy shows, that, while the structure is static at 193 K, dynamic exchange of the donor functions of chelating and terminally bonded ligands occurs at higher temperature. TripodFe(1)2, 2, is obtained from a 1:1:2 mixture of tripod, Fe(II)aq (BF4)2, and Na1-2H2O . With a stoichiometry 1:1:1 of these ingredients and an additional naif equivalent of sodium cyanide, the dinuclear compound [tripodFe{μ-NCC(COOEt)CHC(COOEt)CN}2{μ-CN}Fetripod]BF4, 3 BF4, is obtained. The structure of 3+ shows a helical arrangement of the ligands 1- around the Fe···Fe axis which is a consequence of the incomensurability of the bridging ligands 1- and μ-CN. The two iron centers in 3BF4 differ by their coordination to the carbon or to the nitrogen terminus of the bridging cyano group. This difference is reflected by the NMR spectra, Mössbauer spectra and cyclovoltammograms
Synthese Und Kristallstrukturen Von Chlorometallaten [M = V(III), Mo(V)]
Authors: Chitsaz Soheila , Iravani Effat , Pauls Jochen , Neumüller Bernhard
Published: February 2015

[(THF)2LiCl2VCl2(THF)2] (1) and [Li(THF)4][OMoCl4(THF)] (2) can be prepared by the reactions of VCI3 with LiCl in THF and of Li(H)PtBu with OM0 CI4 in THF, respectively. 1 and 2 were characterized by IR spectroscopy, MS spectrometry (2) and X-ray crystallography. 1 can be obtained in two modifications depending on the temperature of crystallization. At -30 °C a triclinic form, 1a, was isolated from THF solution with one unique molecule per asymmetric unit. However, at 20 °C, 1b crystallized in the monoclinic space group P2/c. It possesses four independent molecules per asymmetric unit. According to the structure analyses 1 consists of a dinuclear complex with a planar LiCl2V four-membered ring while 2 consists of seperate ions [Li(THF)4]+ and [OMoCl4(THF)]-
Chloroisosulochrin, Chloroisosulochrin Dehydrate, And Pestheic Acid, Plant Growth Regulators, Produced By Pestalotiopsis Theae
Authors: Shimada A. , Takahashi I. , Kawano T. , Kimurab Y.
Published: February 2015

New plant growth regulators, named chloroisosulochrin, chloroisosulochrin dehydrate and pestheic acid, have been isolated from the culture filtrate of Pestalotiopsis theae grown on a Raulin-Thom medium. Their structures have been established by spectroscopic and chemical methods. The biological activities of these compounds have been examined using bioassay methods with lettuce and rice seedlings
Secondary Bonding Interactions in Some Halopyridinium and Dihalopyridinium Halides
Authors: Frey Matthias , Jones Peter G.
Published: February 2015

The packing motifs of 2-and 3-chloropyridinium chloride can be interpreted in terms of classical hydrogen bonds N+-H···Cl- and non-classical C-H···Cl-" interactions, with halo-gen-halogen contacts playing a subordinate role. In the corresponding bromine derivatives, Br···Br interactions are much more important. Of the dihalo derivatives, 3,5-dichloropyridinium chloride crystallises with classical linear hydrogen bonds of the form N+-H···Cl- , but its chlorine-chlorine interactions are at best weak; the corresponding bromine derivative displays aggregates of bromine atoms and three-centre hydrogen bonds N+-H (···Br-)2 .
29Si-29Si and 29Si-13C Indirect Nuclear Spin-Spin Coupling, and Isotope-Induced Chemical Shifts 1Δ 12/13C(29Si) and 1Δ 28/29Si(13C), Determined for Silenes Stabilized by Intramolecular N-Si Coordination
Authors: Wrackmeyer Bernd , Oehme Hartmut
Published: February 2015

Silicon, Silenes Two intramolecularly donor-stabilized silenes, l-(8-dimethylamino-l-naphthyl)-l,2,2-tris-(trimethylsilyl)silene (1), and l-[bis-2 ,6 -(dimethylaminomethyl)phenyl]-l,2 ,2 -tris(trimethyl-silyl)silene 2, were studied by 2 9 Si and C NMR spectroscopy, using polarization transfer techniques in order to determine coupling constants V (2 9 Si,2 9 Si) in = 1,2, 3) and '/ (2 9 Si,l3 C) together with isotope-induced chemical shifts 1 zA12/l3 C(2 9 Si) and Z\2 8 / ~9 Si(C).