bluuebunny/crossref_metadata_2025 huggingface dataset:
Luminescence Quenching and Photooxidation of Trichlorostannate(II) by Oxygen
Authors: Becht Alexander , Vogler Arnd
Published: February 2015

The luminescence of [SnCl3]- in acetonitrile (τ= 1.6 μs) is quenched by oxygen with k = 3.8x108 L mol-1 s-1. This quenching is associated with an electron transfer from [SnCl3]- in its 3P1 sp-excited state to O2. Secondary processes lead to the formation of SnOCl2(CH3CN)n with an overall quantum yield of φ = 1.5 at λirr = 254 nm. While this Sn(IV) complex is not light sensitive, [SnCl6]2- in CH3CN undergoes a photochemical reductive elimination with the generation of [SnCl3]- with φ - 0.015 at λirr = 254 nm
Pd(II) and Pt(II) Complexes of 1,2-Bis(pyridin-2-yl)ethane-N,N'
Authors: McFarlane A. , Lusty J. R. , Fiol J. J. , Terrón A. , Molins E. , Miravitlles C. , Moreno V.
Published: February 2015

X-ray crystal structures and properties of the two Pd(II) and Pt(II) complexes [bpeH2][PdCl4] and [Pt(bpe)Cl2], [bpe = 1,2-bis(pyridin-2-yl)ethane] are described and correlated with the IR and 1H NMR/13C NMR spectroscopic data. In the case of the Pt(II) complex, the 1,2-bis(pyridin-2-yl)ethane is bound to the metal by the heterocycle nitrogen atoms but no direct bond is found in the case of the Pd(II) complex. The ligand exhibits low energy geometries in both compounds: the cis-conformation in the Pt(II) complex, and the transconformation in the Pd(II) complex
(Hydroxymethyl)diphenyl(piperidinoalkyl)silane des Typs (HOCH2)(C6H5)2Si(CH2)nNC5H10(n=2,3) und deren Methoiodide: Synthese, Struktur und antimuscarinische Eigenschaften / (Hydroxymethyl)diphenyl(piperidinoalkyl)silanes of the Type (HOCH2)(C6H5)2Si(CH2)nNC5H10(n = 2,3) and their Methiodides: Synthesis, Structure and Antimuscarinic Properties
Authors: Tacke Reinhold , Kropfgans Martin , Tafel Andrea , Wiesenberger Frank , Sheldrick William S. , Mutschler Ernst , Egerer Hansjörg , Rettenmayr Nikola , Gross Jan , Waelbroeck Magali , Lambrecht Günter
Published: February 2015

Starting from (MeO)3SiCH2Cl (10) and Ph2(H)SiCH2OH (16), respectively, the (hydroxymethyl)diphenyl(piperidinoalkyl)silanes (HOCH2)Ph2Si(CH2)2NC5H10 (6) and (HOCH2)Ph2Si(CH2)3NC5H10 (8) have been synthesized [10→Ph2(MeO)SiCH2Cl (11)→Ph2(CH2=CH)SiCH2Cl (12)→Ph2(CH2=CH)SiCH2OAc (13)→Ph2(CH2=CH)SiCH2OH (14)→Ph2(CH2=CH)SiCH2OSiMe3 (15)→6; 16→Ph2(H)SiCH2OSiMe3 (17)→8; NC5H10 = piperidino]. N-Quaternization of 6 and 8 with MeI gave the corresponding methiodides 7 and 9, respectively. As shown by IR-spectroscopic studies, compounds 6 and 8 form intramolecular O-H···N hydrogen bonds in solution (CCl4). In the crystal, 6 (space group Pna21; two crystallographically independent molecules) also forms intramolecular O-H···N hydrogen bonds whereas 8 (space group P1̅) forms intermolecular O-H···N hydrogen bonds leading to the formation of centrosymmetric dimers (single-crystal X-ray diffraction studies). The (hydroxymethyl) silanes 6-9 and the related silanols (HO)Ph2Si(CH2)2NC5H 10 (sila-pridinol; 1), sila-pridinol methiodide (2), (HO)Ph2Si(CH2)3NC5H10 (sila-difenidol; 3) and sila-difenidol methiodide (4) were investigated for their antimuscarinic properties. In functional pharmacological experiments as well as in radioligand competition studies, all compounds behaved as simple competitive antagonists at muscarinic M1-, M2-, M3- and M4-receptors. In general, the silanols 1-4 displayed higher receptor affinities (up to 100-fold) than the corresponding (hydroxymethyl) silanes 6-9 . In the (hydroxymethyl)silane series, compound 7 was found to be the most potent muscarinic antagonist [pA2/pKi= 8,71/8,6 (M1), 8,23/7,8 (M2), 8,19/7,8 (M3); pKi = 8,2 (M4)]. In the silanol series, the related compound 2 showed the most interesting antimuscarinic properties [pA2/pKi = 10,37/9,6 (M1), 8,97/8,8 (M2), 9,08/8,8 (M3); pKi = 9,4 (M4)].
1,3-DipoIare Cycloaddition von Dinitronen - Bildung tricyclischer Dimerer / 1,3 -Dipolar Cycloaddition of Dinitrones - Formation of Tricyclic Dimers
Authors: Aurich Hans Günter , Chair Abdellatif
Published: February 2015

Abstract Various dialdehydes (1 -5) were formed by addition of dithiols to acrolein. Reaction of these dialdehydes with N-alkylhydroxylamines afforded dinitrones the two nitrone groups of which were joined by an alkylidene chain containing two sulfur atoms (6a,b-10a,b). Cycloaddition of these dinitrones with dimethyl acetylenedicarboxylate proceeded in the usual way giving bis(4-isoxazolines) (11a-15a).

However, analogous dinitrones formed by reaction of the dialdehydes with N-(4-tert-butylphenyl)

hydroxylamine could not be isolated. Instead tricyclic compounds arose in which

the central macrocyclic ring is flanked by two isoxazolidine rings (16c-20c). Obviously, the

dinitrones formed as intermediates underwent dimerization with formation of the tricyclic

compounds by cycloaddition between two nitrone groups and two tautomeric N-hydroxyenamine

moieties.

Two of the tricyclic compounds (16c and 20c) formed 1:1 complexes with NiCl2 and FeCl3,

respectively.
RbTe6, ein Polytellurid mit Schichtstruktur 2
∞[Te6
-] / RbTe6, a Polytelluride with Layer Structure 2
∞[Te6
-]
Authors: Sheldrick W. S. , Schaaf B.
Published: February 2015

Reaction of Rb2CO3 with Te in Methanol at 160 °C in the presence of Ge yields the polytellu­ ride RbTe6, the structure of which has been deter­mined by X-ray structural analysis. The poly­anions 2
∞[Te6
-] contain Te6 rings with a chair conformation, which are connected via four Te-Te bonds into a layer structure. A T structure is exhibited by the resulting TeTe3 units. The Rb cations adopt positions between neighbouring parallel anion layers and are surrounded by 12 Te atoms in their first coordination sphere.
Der zweikernige Fe(III)-Komplex von N,N,N',N'-Tetrakis(2-pyridylmethyl)-2-hydroxy-1,3-diaminopropan - Molekül- und Kristallstruktur und seine Wechselwirkung mit Montmorillonit / The Binuclear Fe(III) Complex of N,N,N',N'-Tetrakis(2-pyridylmethyl)-2-hydroxy-1,3-diaminopropane - Molecular and Crystal Structure and its Interaction with Montmorillonite
Authors: Weiss Armin , Dick Stefan
Published: February 2015

Yellow crystals of [Fe2(HPTP)(OH)(NO3)2](Cl04)2 (HPTP = N,N,N',N'-tetrakis(2-pyridyl- methyl)-2-hydroxy-1,3-diaminopropane) were grown by slow diffusion of diethylether into a solution of the complex salt in acetonitrile. Crystal data: space group R3̅, a = 4280,1(15) pm, c = 1147,6(7) pm, Z = 18. The complex exhibits a binuclear Fe(III) core with (μ-oxo)(μ-alkoxo) ligands as bridging units. The nitrate anions coordinate each with a short and a long Fe-O bond. The coordination spheres of the iron atoms can be looked at as distorted edge-shearing pentagonal bipyramides.

The complex cation was introduced into the interlayer region of montmorillonite by cation exchange in acetonitrile. The results of X-ray, IR- and UV/VIS experiments suggest that the cation exchange is reversible. In the interlayer region the dinuclear cations are arranged in a rather loosely packed way, thus creating channels similar to those in pillared smectites or zeolites, respectively.
Mößbauer-Untersuchung ferrimagnetischer Spinelle des Systems CdϰNi1-ϰFe2O4 / Mößbauer Investigation of Ferrimagnetic Spineis in the System CdϰNi1-ϰFe2O4
Authors: Riedel E. , Prick D. , Wolska E.
Published: February 2015

Room temperature Mößbauer spectra of ferrimagnetic spinels in the system Cdϰ
2+Fe1-ϰ
3+[Ni1-ϰ
2+Fe1-ϰ
3+]O4 have been interpreted using the polyhedron model which is based on six different environments at the A-site for the B-site Fe3+-ions. To each environment belongs one sextet with a characteristic magnetic splitting. An additional sextet is due to Fe3+-ions at the A-site.
Dimorphic ThNi2P2 with BaCu2S2 and CaBe2Ge2 Type Structure
Authors: Albering Jörg H. , Jeitschko Wolfgang
Published: February 2015

Two modifications of ThNi2P2 were prepared in a tin flux at 850 °C (α-ThNi2P2) and 1000 °C (β-ThNi2P2). The crystal structures of both modifications were refined from single­crystal X-ray data. α-ThNi2P2 (BaCu2S2 type structure): Pnma. a = 819.69(5), b = 394.28(3), c = 981.54(7) pm. R = 0.028 for 32 variables and 654 structure factors: β-ThNi2P2 (CaBe2Ge2 type structure): P4/nmm, a = 408.5(1), c = 908.0(3) pm, R = 0.033 for 15 variable parameters and 261 F values. Although the two structures are closely related, they can be transformed into each other only by a reconstructive phase transformation. The differences and similari­ties of the two structures are discussed. The high temperature form has higher symmetry, a smaller number of variable positional parameters, and a tendency for higher coordination numbers.
Preparation and Crystal Structure of the Carbides Ln12Re5C15 (Ln = Y, La-N d, Gd-Er)
Authors: Pöttgen Rainer , Block Günter , Jeitschko Wolfgang , Behrens Ronald K.
Published: February 2015

The title compounds were prepared by arc-melting of the elemental components and sub­sequent annealing. Their crystal structure is hexagonal P 6̅ 2 m with one formula unit per cell. It was determined from single-crystal X-ray data of La12Re5C15 (a =1116.8(1) pm, c =545.3(1) pm, R = 0.060 for 287 structure factors and 27 variable parameters) and Ho12Re5C15 (ia = 1066.7(1) pm, c = 504.2(1) pm, R = 0.018 for 392 F's and 31 variables). The structures correspond to the formula Ln12[ReC3]2[Re3C3(C2)3],where the brackets indicate two differ­ent trigonal planar anionic rhenium-carbon groups. The coordination of the rhenium atoms in these polyanions seems to be compatible with the 18-electron rule.
Kristallstruktur und Schwingungsspektren von Zn(NH3)4(ClO4)2 / Crystal Structure and Vibrational Spectra of Zn(NH3)4(ClO4)2
Authors: Hillebrecht Harald , Thiele Gerhard , Koppenhöfer Alrik , Vahrenkamp Heinrich
Published: February 2015

The title compound Zn(NH3)4(ClO4)2 crystallizes in the space group F4̄3m with a = 10.240(1) Å. The crystal structure consists of tetrahedral Zn(NH3)4 cations and two nonequivalent ClO4 anions with crystallographic Td symmetry. The complex ions constitute an arrangement which is known from the Zintl phase MgAgAs. The Zn(NH3)4 cations are ccp packed with perchlorate anions in octahedral and tetrahedral voids. Whereas the ClO4 ions centered at tetrahedral holes do not interact with the other lattice components, the perchlorate ions in the octahedral voids are connected with the ammine ligands by a hydrogen bonded three-dimensional network involving all their N, H, and O atoms. The repeating unit of this network is a N4O4(μ-H)12 cube with N-H = 1.19(2) Å and O···H = 1.98(2)Å . Raman and IR spectra were recorded between 150 and 4000 cm-1. All the expected internal modes of the complex ions could be detected and assigned. The crystallographically different ClO4 anions have nearly the same vibrational spectra, only a slight splitting of two IR modes is observed
Synthesis and Structure of Tetraethylcyclotetraarsathiane and its Complexes [Ag{cyclo-(C2H5AsS)4}2]CF3SO3 and [cyclo-(C2H5AsS)4]·2SbBr3
Authors: Häusler Thomas , Sheldrick William S.
Published: February 2015

Ethylcycloarsathiane (C2H5AsS)n crystallizes as a crown-shaped cyclotetramer 1 from a chloroform/pyridine solution. 1H and 13C NMR studies indicate the presence of two major oligomers in CHC13 solution in an approximately 1:1 ratio. Reaction of 1 with AgCF3SO3 yields [Ag{cyclo-(C2H5AsS)4}2]CF3SO3 (2) in which the silver (I) cation exhibits a distorted quadratic-antiprismatic coordination geometry with four shorter (2.716(7), 2.767(5) Å) and four longer (3.218(6), 3.328(9) Å) Ag-S distances. The tetraethylcyclotetraarsathiane ligand exhibits a K1S coordination mode in the complex [cyclo-(C2HsAsS)4]·2SbBr3 (3) with the sulphur atom adopting an axial positon in a ψ-trigonal bipyramidal antimony coordination polyhedron
Structural Characterization of Dihydroselenapyrans Prepared by the Reaction of Diarylselenoketones with Conjugated Dienes
Authors: Fröhlich Roland , Grehl Matthias , Wilker Stefanie , Erker Gerhard , Mazerolles Pierre , Laurent Christian
Published: February 2015

Diarylselenoketones Ar1Ar2C=Se (2b: Ar1 = C6H5, Ar2 = -p-C6H4Cl; 2c: Ar1 = Ar2 = -p-C6H4F) were generated by treatment of the corresponding ylides with elemental selenium (“Staudinger-Chalcogenation”) and trapped with 2,3-dimethylbutadiene and 3,4-bis(methylene)-1,1-diphenyl-1-germacyclopentane, respectively, to yield the substituted 2,2-diaryl-3,6-dihydro-2H-selenapyrans 5b and 5c. The compounds 5b and 5c were characterized by X-ray crystal structure analyses.
Ho4C7, Y4C7: Carbide mit C3
4-- und C4- -Ionen / Ho4C7, Y4C7: Carbides with C3
4- and C4- Ions
Authors: Mattausch Hansjürgen , Gulden Thomas , Kremer Reinhard K. , Horakh Jörg , Simon Arndt
Published: February 2015

The new compounds Ho4C7 and Y4C7 have been prepared by reaction of stoichiometric amounts of the metals and C in closed Ta capsules at 1450 and 1300 K. respectively. With HoF3 as a flux, black, needle like single crystals of Ho4C7 were obtained, which are air and moisture sensitive. Ho4C7 crystallizes in the space group P21/n (No. 14) with lattice constants a = 368.06(3), b = 1251.8(1). c = 1364.4(2) pm and β = 96.62(1)°. Y4C7 with a = 370.08(5), b = 1258.9(1), c = 1371.8(1) and β = 96.61(1)°.

Two different kinds of carbon species occur in the two structures: isolated C4- ions and C3
4- units, respectively. The C4- ions are octahedrally surrounded by Ho-atoms. The Ho6C octahedra are condensed to form double chains parallel [100]. The chains are linked via C3
4- ions, which occupy positions above the edges of the Ho octahedra. Additional Ho atoms are located in voids between the C3
4- units.

The compounds are electrically semiconducting. Ho4C7 has a magnetic Curie-Weiss behaviour with θ= -28(4) K and µeff= 8.8(2) µB.
Zur Struktur von Dihydroxonium Alkandisulfonaten / The Structure of Dihydroxonium Alkanedisulfonates
Authors: Sartori Peter , Jüschke Ralf , Boese Roland , Bläser Dieter
Published: February 2015

The crystal structures of methanedisulfonic acid-(1) and 1,2-ethandisulfonic acid-dihydrate (2) have been determined from single crystal X-ray diffraction at T = 145 K (for 1) and T = 125 K (for 2). It has been found, that both acids exist in an ionic form as dihydroxonium sulfonates, but differ in the geometry of the sulfonate groups and in the positions of the hydrogen atoms at the oxonium ions.
Radikalreaktionen von 6,6-DimethylfuIven am paramagnetischen Cobalt(0)-Zentrum -Struktur eines Dicobaltkomplexes mit tetramerem Kohlenwasserstoff-Liganden / Radical Reactions of 6 ,6 -Dimethylfulvene at Paramagnetic Cobalt(O) Centers - Structure of a Dicobalt Complex Containing a Tetrameric Hydrocarbon Ligand
Authors: Klein Hans-Friedrich , Auer Emmanuel , Jung Thomas , Röhr Caroline , Kniep Rüdiger
Published: February 2015

6,6-Dimethylfulvene reacts with Co(C2H4)(PMe3)3 to give a diamagnetic dicobalt complex containing a novel bis (η5,η2)-chelating hydrocarbon ligand which is a tetramer of 6,6-dimethylfulvene. C,C-coupling via radicals induces multiple chirality in the ligand and the structurally characterized stereoisomer adopts a (S,R,R,S) configuration (m eso form).
Zinkkomplexe von Sulfonamiden / Zinc Complexes of Sulfonamides
Authors: Hartmann Uwe , Vahrenkamp Heinrich
Published: February 2015

The diuretic sulfonamides furosemid (H2Fur) and hydrochlorothiazid (H2Hyt) were used as ligands in zinc complexes. Spectroscopic data indicate that in [(HFur)Zn(H2O)2]ClO4 and (HFur)2Zn the furosemid ligand is bound to zinc via its carboxylate and amine functions while (Fur)Zn(NH3)2 is a coordination polymer with Zn-carboxylate and Zn-sulfonimide coordination. A structure determination shows (Hyt)Zn(NH3)2 to be a coordination polymer as well, with both deprotonated sulfonamide functions forming Zn-N bonds.
Die Pd-katalysierte oxidative Kupplungsreaktion von Methylbenzoesäuremethylester / The Pd-Catalyzed Oxidative Coupling Reaction of Methyl Methylbenzoates
Authors: Shiotani Akinori
Published: February 2015

The Pd-catalyzed oxidative coupling reaction of methyl o-toluate gives, in the presence of a Pd/1,10-phenanthroline(phen)/Cu catalyst, exclusively, the para-linked biphenyldicarboxylates 1, 2, and 3. On the other hand, the meta-linked biphenyldicarboxylates 4 and 5, were predominantly formed in a catalyst system of Pd/2,4-pentanedione(acacH)/Cu, and under similar conditions 6 and 7 were also obtained from the coupling reaction of methyl m-toluate and methyl p-toluate, respectively. A reaction scheme has been proposed.
Calorimetrie an Yttriumtrihalogeniden und Yttriumoxidhalogemden / Calorimetry of Yttrium Trihalides and Yttrium Oxyhalides
Authors: Oppermann H. , Ehrlich S. , Hennig C.
Published: February 2015

The heats of solution of Yttrium, YOCL, YOBr, YOI, YCl3, YBr3, YI3 and Y2O3 were determined in 4n HX. From those the enthalpies of formation of Yttrium Trihalides YX3 and Yttrium Oxyhalides YOX at 298 K were derived:

ΔHB
0(YCl3,f,298) = -240.4 ± 0.6 kcal/mol, ΔHB
0(YBr3,f,298) = -202.1 ± 1.5 kcal/mol,

ΔHB
0(YI3,f ,298) = -147.0 ± 1.7 kcal/mol, ΔHB
0(YOClf,298) = -240.2 ± 1.0 kcal/mol,

ΔHB
0(YOBrf,298) = -229.7 ± 2.0 kcal/mol, ΔHB
0(YOIf ,298) = -208.8 ± 2.0 kcal/mol.
Synthese und Kristallstruktur von Pentakis(dimethylsulfoxid)- oxo-titan(IV)chlorid / Synthesis and Crystal Structure of Pentakis(dimethylsulfoxide)-oxo-titanium(IV) Chloride
Authors: Enders M. , Rudolph R. , Pritzkow H.
Published: February 2015

Pentakis(dimethylsulfoxide)-oxo-titanium(IV) chloride is obtained by reaction of titanium tetrachloride with a stoichiometric amount of water in dimethylsulfoxide. A single crystal structure determination (P1̄, a = 9.564(6), b = 10.504(7), c = 12.510(8) Å, α = 70.21(5), β = 83.48(5), γ = 89.82(5)°, V = 1174 Å3, Z = 2) shows a dicationic titanium(IV) complex with five dimethylsulfoxide ligands and one oxygen atom. The two chlorine anions are not bonded to the complex cation. The TiO6-fragment is a distorted octahedron, where five of the six oxygen atoms belong to the coordinated dimethylsulfoxide molecules.
Thermochemische Untersuchungen zum ternären System Bi/Se/O. II. Das Teilsystem Bi2O3– SeO2/Thermochemical Investigations on the Ternary System Bi/Se/O.II.The Binary System Bi2O3–SeO2
Authors: Oppermann H . , Göbel H . , Schadow H . , Schmidt P. , Hennig C. , Vassilev V. , Markova-Deneva I.
Published: February 2015

We describe the existence of six thermodynamically stable phases on the binary line Bi2O3- SeO2 at room temperature: Bi12SeO20, Bi10Se2O19, Bi16Se5O34, Bi2SeO5, Bi2Se3O9 and Bi2Se4O11. At higher temperature we optained evidence for Bi20Se3O36 and Bi4SeO8. The decomposition pressures were measured for all phases in a membrane zero manometer and the enthalpy of formation and the standard entropy was determined. The phase barogram and phase diagram followed from total pressure measurements and differential thermoanalysis. The standard enthalpies of formation of all phases were also derived from solution calorimetry. The necessary data of transitions on molar enthalpies were obtained by DSC- and Cp-measurements.
Thermochemische Untersuchungen am System Bi/Se/O III. Zum quasibinären System Bi2O3 –Bi2Se3 und zum ternären Bereich Bi2O3– Bi2O2Se – Se – SeO2/Thermochemical Investigations on the System Bi/Se/O III.The Quasy Binary System Bi2O3-Bi2Se3and the Ternary Range Bi2O3-Bi2O2Se–Se–SeO2
Authors: Oppermann H. , Göbel H. , Schmidt P. , Schadow H. , Vassilev V.
Published: February 2015

Only the ternary phase Bi2O2Se is shown to exists in the thermodynamical equilibrium in the investigated ternary system on the binary line Bi2O3-Bi2Se3. Its thermal decomposition was measured in a quartz membrane zero manometer. The enthalpy of formation and the standard entropy were derived from the temperature function of the decomposition equilibrium:

⊿H°f(Bi2O2Ses,298) = -104,6 ±4,0 kcal/mol

S°(Bi2O2Ses,298) = 43 ± 3 cal/K·mol.

The coexistence ranges in the ternary region Bi2O3- SeO2- Bi2O2Se-Se were followed by X-ray diffraction, IR spectroscopy and total pressure measurements of binary and ternary compositions.
Synthese, Struktur und Reaktivität von 3-Triorganostannyl-N-diphenylmethylen-alaninestern / Synthesis, Structure and Reactivity of 3-Triorganostannyl-N-diphenylmethylenealanine Esters
Authors: Dölling Karin , Merzweiler Kurt , Wagner Christoph , Weichmann Horst
Published: February 2015

The deprotonation of N-diphenylmethylene-glycine esters, obtained from glycine ester hydrochlorides and benzophenone imine, and reaction of the resulting carbanions with iodomethyl triorganostannanes gives the 3-triorganostannyl-N-diphenylmethylene-alanine esters Me2RSnCH2CH(N=CPh2)COOR′ (1a - e; R = Me, tBu; R′ = Me, Et, tBu, Bz). These title compounds are transformed into their tin monochlorides MeR(Cl)SnCH2CH(N=CPh2)COOR′ (2a - e) by a redistribution reaction with Me2SnCl2. IR and NMR data and the crystal structure of Me2(Cl)SnCH2CH(N=CPh2)COOEt (2b) reveal for 2a - e an intramolecular coordination of the ester C = 0 group at the tin atom. Mild two-phase hydrolysis of 1a - e with 1N HCl gives the 3-triorganostannyl-alanine ester hydrochlorides Me2RSnCH2CH(NH2)COOR′ · HCl (3a - e). The transformation of 3a - e into the corresponding alanine esters Me2RSnCH2CH(NH2)COOR′ (4a - e) could be realized with NH3 in chloroform. 4a - e are of limited thermal stability.
Hexahydro-closo-hexaborate as a Ligand in Coordination Compounds: A Second Polymorph of [Au2(μ-bis-η3-B6H6)(PPh3)2]
Authors: Schaper T. , Näther C. , Preetz W.
Published: February 2015

The crystal structure of a second room-temperature polymorph of the complex [Au2(μ-bis-η3-B6H6)(PPh3)2] is presented and compared with the previously reported phase. The change of the solvent which is layered on a solution of [Au2(μ-bis-η3-B6H6)(PPh3)2] in CH2CI2 from petroleum ether to n-pentane leads to a second form with fundamental differences in the crystal structure. Instead of the octahedrally shaped crystals, space group Pa3̄, the crystals in the present determination are orthorhombic needles crystallizing in space group Pccn with a remarkable increased calculated density from 1.326 to 1.855 Mg/m3.
Darstellung und spektroskopische Charakterisierung von Methylnitro-closo-hexaboraten sowie Kristallstrukturen von cis-(Ph4As)2[B6H4(CH3)(NO2)],fac-(Ph4As)2[B6H3(CH3)(NO2)2] · CH3CN und mer-(Ph4P)2[B6H3(CH3)(NO2)C2] / Synthesis and Spectroscopic Characterization of Methylnitro-closo-hexaborates and Crystal Structures of cis -(Ph4As)2[B6H4(CH3)(NO2)],fac-(Ph4As)2[B6H3(CH3)(NO2)2] · CH3CN and mer-(Ph4P)2[B6H3(CH3)(NO2)C2]
Authors: Drewes C. , Preetz W.
Published: February 2015

By electrochemical oxidation of (n-Bu4N)[B6H6(CH3)] in the presence of nitrite ions and of the base DBU in dichloromethane solution cis- and trans-[B6H4(CH3)(NO2)]2- , fac- [B6H3(CH3)(NO2)2]2- and mer-[B6H3(CH3)(NO2)c
2]2- are formed. X-ray diffraction analyses have been performed on single crystals of cis-(Ph4As)2[B6H4(CH3O)(NO2)] (1) (monoclinic, space group P21/a, a = 20.063(2), b = 10.858(1), c =21.384(2) Å, β = 105.818(9)°, Z = 4), fac-(Ph4As)2[B6H3(CH3)(NO2)2] ·CH3CN (2) (triclinic, space group P1̄, a = 10.333(3), b = 10.695(3), c = 22.833(6) Å, α = 93.91(3), β = 96.79(3), γ = 104.56(2)°, Z = 2), and mer-(Ph4P)2[B6H3(CH3)(NO2)c
2] (3) (triclinic, space group P1̄, a - 10.100(1), b = 10.402(3), c = 22.923(3) Å, α = 96.328(18), β = 89.928(12), γ = 107.963(16)°, Z = 2). The 11B NMR spectra and the vibrational spectra of the methylnitro compounds are discussed and compared with those of the monomethyl- and mononitro-closo-hexaborates.
Direct Oxidative Deprotection of Trimethylsilyl and Tetrahydropyranyl Ethers Using Alumina-Supported lodobenzene Diacetate under Non-Aqueous Conditions
Authors: Heravi Majid M. , Tajbakhsh Mahmood , Ghassemzadeh Mitra
Published: February 2015

Primary and secondary trimethylsilyl and tetrahydropyranyl ethers are converted to their carbonyl compounds efficiently using alumina-supported iodobenzene diacetate.
Untersuchungen zur Trifluoracetylierung der Methylderivate von Tryptamin und Serotonin mit verschiedenen Derivatisierungsreagentien: Synthesen, Spektroskopie sowie analytische Trennungen mittels Kapillar-GC / Trifluoroacetylation of Methylated -Derivatives of Tryptamine and Serotonine by Different Reagents: Synthesis, Spectroscopic Characterizations, and Separations by C apillary-Gas-Chromatography
Authors: Häfelinger Günter , Nimtz Manfred , Horstm Volker , Benz Thomas
Published: February 2015

Die Trifluoracetylierungs-Reaktionen verschiedener N-Methylderivate des Tryptamins sowie von N- und O-Methylderivaten des Serotonins mit den Derivatisierungsreagentien: Trifluoracetanhydrid, N-Methylbistrifluoracetamid und Trifluoracetylimidazol wurde analytisch mittels Glas-Kapillar-GC untersucht und die Strukturen der trifluoracetylierten Reaktionsprodukte durch GC-MS-Kombination ermittelt. Fünf dieser Trifluoracetylderivate wurden außerdem präparativ dargestellt und durch MS, IR, 1H, 13C und 19F NMR-Spektren charakterisiert. Im Gegensatz zu Literaturangaben lassen sich die physiologisch interessanten Indolethylamine mit einer tertiärer Dimethylaminoseitenkette (z.B. DMT und Bufotenin) nicht unter den gleichen Reaktionsbedingungen wie bei den anderen Methylderivaten trifluoracetylieren, da die tertiäre Aminogruppierung eine Trifluoracetylierungsreaktion eingeht. Das entsprechende nichtflüchtige N-trifluoracetylierte Produkt wurde von uns präparativ isoliert und spektroskopisch eindeutig charakterisiert.
Dichloro[bis(η5-2,4-cyclopentadien-l-yl)alkylphosphan]zirconium: PR(C5H4)2ZrCl2; R = Me, Et, iPr, tBu / Dichloro[bis(η5-2 ,4 -cyclopentadien-l-yl)alkylphosphine]zirconium: PR(C5H4)2ZrCl2; R = Me, Et, iPr, tBu
Authors: Häp Markus , Gilles Theo , Kruck Thomas , Tebbe Karl-Friedrich
Published: February 2015

A series of new ansa-zirconocene dichloride compounds [PR(C5H4)2ZrCl2; R = Me (5), Et (6), iPr (7), tBu (8)] with phosphorus as bridging atom between the cyclopentadienyl rings have been prepared, isolated, and characterised by 1H, 13C, 31P NMR spectroscopy, mass spectrometry and elemental analysis. The X-ray structure of 5 is reported.
Montmorillonite K-10 Catalyzed Knoevenagel Condensation under Microwave Irradiation in Solventless System
Authors: Heravi Majid M. , Tajbakhsh Mahmood , Mohajerani Bagher , Ghassemzadeh Mitra
Published: February 2015

Montmorillonite K-10 catalyzed efficiently the Knoevenagel condensation of carbonyl compounds with malonitrile and ethylcyanoacetate in dry media under microwave irradiation.
New Monoterpene Glycosides from Paeonia emodi
Authors: Muhammad Pir , Ahmad Saeed , Rubnawaz Hafiz , Ullah Nisar , Malik Abdul
Published: February 2015

Two new monoterpene glycosides, wurdin and benzoylwurdin along with known compounds, paeoniflorin. lactiflorin and oxypaeoniflorin have been isolated from Paeonia emodi. The identity of new compounds have been established by a combination of spectroscopic techniques and chemical transformations.
Synthese und Molekülstruktur des [α-(Dichlormethylsilyl)ethyl]- dichlorboran-dimethylsulfid / Synthesis and Molecular Structure of [α-(Dichloromethylsilyl)ethyl]- dichloroborane-dimethylsulfide
Authors: Ruwisch Lutz , Riedel Ralf , Klingebiel Uwe , Noltemeyer Mathias
Published: February 2015

[α-(Dichloromethylsilyl)ethyl]-dichloroborane-dimethylsulfide has been synthesized by the reaction of dichloromethylvinylsilane with dichloroborane-dimethylsulfide and its molecular structure determined by single crystal X-ray diffraction and by spectroscopic methods. Following the Markovnikov rule, a chiral methine group is formed as a bridge between silicon and boron.
Neighbouring Group Participation of C-6 Substituents of Glucose Derivatives on the Stereoselectivity of the N-Glycosidic Linkage of Glycopeptides
Authors: Zhang Hong , Wang Yali , Thürmer René , Parvez Khalid , Choudhary Iqbal , Rahman Atta-ur , Voelter Wolfgang
Published: February 2015

The first example of a glycopeptide with a direct N-α-glycosidic linkage between the trisaccharide and the amino acid residue was found in the glomerular basement membrane of rats. In connection with the total synthesis of nephritogenoside, glycosyl azides with different protecting groups and carbohydrate chain lengths are synthesized, reduced to the corresponding glycosyl amines and coupled with Z-Asp-OBzl. Remarkable differences in the α:β ratio of the condensation products are observed, caused by neighbouring group participation.
Synthese und Kristallstruktur von 3.6-Di-tert-butylpyridazin / Synthesis and Crystal Structure of 3.6-Di-tert-butylpyridazine
Authors: Kuhn Norbert , Kotowski Heike , Steimann Manfred
Published: February 2015

3,6-Di-tert-butylpyridazine (4) is obtained from 2,2,7,7-tetramethyloctan-3,6-dione (2) and anhydrous hydrazine in good yield. Its X-ray structure is reported.
1.2-Verzweigte Carbosiloxan-Dendrimere mit Hauptgruppenelementund Übergangsmetall-modifizierten Oberflächen / 1.2-Branched Carbosiloxane-Dendrimers with Main-Group Element and Transition-Metal Modified Surfaces
Authors: Brüning Karin , Lühmann Bettina , Lang Heinrich
Published: February 2015

The preparation of the first and second generation carbosiloxane dendrimers Si[OCH2- CH2CH2 SiMe(OCH2C=CH)2]4 (3) and Si{OCH2H2CH2SiMe[OCH2CH2CH2SiMe(OCH2 - C=CH)2]2}4 (5) by the reaction o f Si(OCH2CH2CH2SiMeCl2)4 (1) or Si[OCH2CH2CH2SiMe- (OCH2CH2CH2SiMeCl2)2]4 (4) with HOCH2C =CH (2) in the presence o f NEt3 is described. Dendrimers 3 and 5 contain propargyloxy units as terminal groups, which can be transferred to Co2((CO)8 (6) to give the hexacarbonyldicobalt functionalized dendritic molecules Si{OCH2CH2CH2[(η-OCH2C=CH)CO2(CO)6]2}4 (7) and Si{OCH2CH2CH2SiMe-(OCH2CH2CH2SiMe[(η-OCH2C=CH)CO2(CO)6]2)2}4 (8).

All compounds were characterized by elemental analyses, spectroscopic studies (IR,1H-, 13C{1H }-, 29Si{1H} NMR) as well as GPC investigations
Darstellung, 11B-NMR- und Schwingungsspektren von c/s-Monoethylmononitrotetrahydro- c/050-hexaborat(2-) sowie Kristallstruktur von cis (Ph4As)2[B6H4(C2H5)(NO2)] / Synthesis, 11B NMR and Vibrational Spectra of cis-Monoethylmononitrotetrahydroc-closo-hexaborate(2-) and Crystal Structure of cis-(Ph4As)2[B6 H4 (C2H5 )(NO2)]
Authors: Drewes C. , Preetz W.
Published: February 2015

By electrochemical oxidation of (n-Bu4N)[B6H5Hfac(C2H5)] in the presence of nitrite ions and of the base DBU in dichloromethane solution cis-[B6H4(C2H5)(NO2)]2- is formed. X-ray diffraction analysis has been performed on a single crystal of cis-(Ph4 As)2[B6H4(C2H5)(NO2)] (triclinic, space group P1; a = 10.673(4). b = 10.907(4), c = 21.237(4) A, α = 80.789(4), β = 83.117(4), γ = 66.548(2)°, Z = 2). The 11B NMR spectrum is consistent with a disubstituted octahedral B6 cage with local Cs symmetry. The IR and Raman spectra exhibit characteristic CH3, CH2, NO2, BN, BH and B6 vibrations
Complexes of N-Aryltriphenylphosphinimines with Mercury(II) Halides
Authors: Braun Thomas P. , Gutsch Paul A. , Zimmer Hans
Published: February 2015

The synthesis, IR and 31P NMR spectra of the complexes of various N-aryltriphenylphosphinimines with some mercury dihalides as well as the corresponding phosphonium salts are reported. It is shown by an X-ray crystal structure analysis of the complex of the unsubstituted phosphinimine with HgCl2 that in the solid state these complexes form dimers via two Hg ∙∙∙ μ2- Cl ∙∙∙ Hg bridges.
Serendipitous Formation of the Cyclic Sulfite DIMTH(SO3) by Reaction of DIMTH(OH)2 with SOCl2
Authors: Handrosch Carsten , Heinemann Frank W. , Kisch Horst
Published: February 2015

The reaction of the acetonide protected derivative of tartaric acid, DIMTH(OH)2 (1) (1,6-didesoxy- 3,4-O-isopropylidene-2,5-di-C-methyl-threo-hexitol), with SOCl2/NEt2 does not lead to the expected dichlorinated species 2, but affords the cyclic sulfite DIMTH(SO3) (3) ((1R, 7R)-9,9-dimethyl-4-oxide-2,2,6,6-tetramethyl-4-thia-3,5,8,10-tetraoxabicyclo-[5,3,0] decane) as indicated by X-ray structural analysis.
Synthesis, Reactions and Spectroscopy of 3-Benzoyl-6-phenylpyridazines of Expected Biological Activity
Authors: Issac Yvette A .
Published: February 2015

yielded 3-benzoyl-6-phenylpyridazine (2). Phenyl(6-phenyl-pyridazin-3-yl)methanol (3) has been obtained via NaBH4 reduction of ketone 2. Reaction of 2 with hydroxylamine or its O-alkyl analogue has been found to yield 3-benzoyloxime-6-phenylpyridazine (4) and alkyloximes (5), respectively. Treatment of 4 with a mixture of acetic acid and sulfuric acid afforded ketone 2 again and not the rearranged products (6 or 7). Beckmann rearrangement has however been achieved for 3-benzoyl(O-ethyloxime)-6-phenylpyridazine (5a) and oxime 4 giving solely 3-carboxanilide-6-phenylpyridazine (6), 4-Benzoyloxime-3-phenyl-6-chloropyridazine (17) has been synthesized from the corresponding ketone 16.
Synthetic Potential Inherent in D-Isoascorbic Acid as a Precursor for Pyridazine and Furo[3,2-c]pyridazine Ring Systems with Two Asymmetric Centers
Authors: El Ashry E. S. H. , Awad L. F. , Hamid H. Abdel , El Kilany Y.
Published: February 2015

Reaction of D-erythro-2,3-hexodiulosono-1,4-lactone-2,3-bis(phenylhydrazone) (2) with an iodine, triphenylphosphine and imidazole mixture afforded the furo[3,2-c]pyridazine derivative 11. Condensation of 6-bromo-6-deoxy-D-erythro-2,3-hexodiulosono-1,4-lactone with phenylhydrazine gave the bishydrazones 6, and 8 or the furo[3,2-c]pyridazine (11) depending on the reaction conditions. The lactone ring in 11 could be opened by treatment with alkali to give the pyridazine derivative 9. Lactonization of the later with simultaneous acetylation by acetic anhydride afforded the lactone derivative 14. Alkali treatment of 6 gave the pyrazolindione derivative 13 that gave upon reation with HBr/AcO H the dibromide 15. The assigned structures were based on spectral analysis. The activity of compounds 11 and 14 against hepatitis B virus has been studied.
Chiral Pool Synthesis of 4a-Substituted Carbocyclic Cyclopentanoid Nucleoside Precursors, II
Authors: Csuk René , Dörr Petra , Kühn Martin , Krieger Claus , Irngartinger Hermann , Oeser Thomas , Antipin Mikhael Yu.
Published: February 2015

Suitable protected 4,4a-anhydro-cyclopentane derivatives have been used for the straightforward of cyclopentanoid nucleoside precursors. Thus, by simple transformations nucleoside precursors modified at the positions C(4), C(4a) and C(4,4a) as well as side-chain modified derivatives were accessible. The structures of the key intermediates were determined by xray analyses.
Crystal and Molecular Structure of the Copper(I)-thiolate-selenide Complex [Ph4P][Cu(SeS2CNC4H8)(S2CN2C4H8)] with an Unusual Se-S Bond
Authors: Zhang Qianfeng , Chen Jinxi , Hong Maochun , Xin Xinquan , Fun Hoong-Kun
Published: February 2015

Reaction of a DMF solution of Cu(S2CNC4H8) with [Ph4P]2[WSe4] affords [Ph4P]2[WSe4- (CuS2CNC4H8)3] (1) and [Ph4P][Cu(SeS2CNC4H )(S2CN2C4H8)] (2) in which a Se atom from the decomposition of the WSe4
2- anion has reacted with the pyrrolidyldithiocarbamate (C4H8dtc) ligand anion to form the new ligand anion SeS2CNC4H8
⊖. Complex 2 crystallizes with four formula units in the monoclinic space group P21/c in a cell of dimensions a = 10.5824(2), b = 18.7575(3), c = 18.3268(4) Å and ß = 109.0980(10)°. 6055 independent reflections above background were measured with a diffractometer and the structure was refined anisotropically to R =0.073. The anion contains a three-coordinated copper(I) atom. The C4H8dtc⊖ ligand is bonded to the Cu+ cation in a terminal fashion, while SeS2CNC4H8
⊖ chelates the Cu+ cation. The Se-S bond length is 2.231 (4) Å.
Reactivity and Structure of Diferrocenylamine and N,N - Diferrocenylcarbamoylchloride
Authors: Bildstein Benno , Malaun Michael , Kopacka Holger , Wurst Klaus
Published: February 2015

The reactivity of diferrocenylamine has been investigated aiming at the preparation of novel diferrocenylamino compounds, including nitrenium salts, amino radicals, transition metal amides, carbamato ligands, and others. However, diferrocenylamine is unexpectedly difficult to derivatize; only simple metalation by butyl lithium, alkylation by iodomethane, and chloroformylation by phosgene were possible. X-ray crystal structures are reported for the starting diferrocenylamine, and for the derivatives diferrocenylmethylamine and N,N diferrocenylcarbamoylchloride.
Beiträge zur Chemie des Phosphors, 242 Tri-tert-butylcyclotriphosphan-monoxid, (PBut )3O - Bildung und 31P-NMR-spektroskopische Strukturbestimmung/ Contributions to the Chemistry of Phosphorus, 242 Tri-tert-butylcyclotriphosphane Monoxide, (PButO — Formation and Structure Determination by 31P NMR Spectroscopy
Authors: Baudler Marianne , Breitkopf Christoph
Published: February 2015

The partially oxidized cyclotriphosphane (PB ut)3O (1,2,3-tri-tert-butyl-1-oxocyclotriphosphane) (1) has been obtained by [2 + 1] cyclocondensation of K (But)P-P(But)K with ButP(O)Cl2 in toluene at -78 °C. The cyclophosphanes (PBut)4 and (PBut)3 as well as small amounts of the open-chain triphosphane [ButP(O)Cl]2P (O)But are also formed. In contrast to the unoxidized compound (PBut)3, compound 1 is not stable at room temperature, but decomposes above -30 °C undergoing rearrangement into the cyclotetraphosphanes (PBut)4 O (2), (PBut)4O2 (3), and (PBut)4. The 31P NMR parameters of 1 and 3 are reported and discussed.
Synthesis and HPLC-Analysis of N-(2-Phenyl-cyclopropyl)-Substituted Chain Elongated Nucleoside Analogues
Authors: Csuk René , Kern Anja , Mohr Kristina
Published: February 2015

A novel class of nucleoside analogues containing adenine, uracil, thymine and 5-fluorouracil as the heterocyclic moieties have been prepared from 2-phenylcyclopropane carboxylic acid. These compounds showed weak antitum or activity. The resolution of the racemates on an analytical and semipreparative scale was performed by HPLC using chiral stationary phases.
6-Pyridyl-1-aza-2λ5,4λ5-diphosphinin - ein 2,2′-Bipyridin-Analogon/ 6-Pyridyl-1-aza-2λ5,4λ5-diphosphinine - a 2,2′-Bipyridine Analogue
Authors: Heckmann Gernot , Plank Stefan , Fluck Ekkehard , Dashti-Mommertz Anahita , Neumüller Bernhard
Published: February 2015

1,1,3,3-Tetrakis(dimethylamino)-1λ5,3λ5-diphosphete, (1), reacts with 2-cyano-pyridine to yield 6- pyridyl-1-aza-2λ5,4A5-diphosphinine (3). 3 is characterized by its 1H , 31P, and 13C NMR, mass, and IR spectra as well as the results of the X-ray structure analysis.
Neue Chalkogenometallate mit binuklearen Anionen, I: Darstellung und Kristallstruktur von Rb6Sn2S7 / New Chalcogenometallates with Binuclear Anions, I: Preparation and Crystal Structure of Rb6Sn2S7
Authors: Klepp Kurt O. , Fabian Ferdinand
Published: February 2015

Colorless crystals of the new thiostannate Rb6Sn2S7 were obtained by reacting a stoichiometric melt of Rb2S, Sn and S at 700°C. The compound is orthorhombic, oP60, s.g. P212121 (No. 19) with a = 9.982(4), b = 13.45(1), c = 15.20(1) Å; Z = 4. The crystal structure was determined from diffractometer data and refined to a conventional R of 0.043 (1380 Fo's, 137 variables). The crystal structure contains dimeric anions, [Sn2S7]2 -, which are built up by slightly distorted SnS4 tetrahedra sharing a common sulfur atom. The mean Sn-S bond length calculates as 2.384 Å, the bond angle on the bridging S is 110.4°. The structure contains six independent Rb-cations which are coordinated to 5-6 sulfur atoms in irregular configurations.
Equilibrium and Structural Study of Chloro Complexes of Iron(III) Ion in Acidic Aqueous Solution by Means of X-Ray Absorption Spectroscopy
Authors: Inada Yasuhiro , Funahashi Shigenobu
Published: February 2015

Using an extended X-ray absorption fine structure (EXAFS) technique, the formation constant of the pentaaquachloroiron(III) complex was determined to be 3.8 ± 0.4 mol-1 dm3 at 25.0 ± 0 .1 °C in a 1.00 mol dm-3 HCIO4 aqueous solution. The structures of [Fe(OH2)6]3+ and [FeCl(OH2)5]2+ were determined on the basis of the same EXAFS data. The Fe-O bond length (2.05 Å) in the latter is longer than that (2.01 Å) in the former due to the electron donation and charge neutralization by the coordinating chloride ion with the Fe-Cl bond length of 2.26 Å.
Darstellung von phosphorylierten Glucosiden durch Umsetzung am Glucosegerüst sowie am Aglycon / Synthesis of Phosphorylated Glucosides through Reaction at the Glucose Framework and at the Aglycon
Authors: Melnicky Carsten , Neda Ion , Schmutzler Reinhard
Published: February 2015

The reaction of Me2P(:X)H [X = O: 1; X = S: 4] with paraformaldehyde furnished the α - hydroxyphosphine oxide 2 and sulfide 5 which, upon treatment with p-toluenesulfonyl chloride, were converted into the tosylated derivatives 3 and 6. The diphosphorylated glucosyl compound 8 was synthesized by reaction of two equivalents of tosylated phosphine oxide 3 with benzyl 4,6- O-benzyliden-α-D-glucopyranoside 7. The spacer phosphorylated glucosyl derivatives 10 and 11 were formed in the reaction of γ -bromopropyl-2,3,4,6-tetra-0 -benzyl-β-D-glucopyranoside 9 with triethylphosphite and triphenylphosphine.
Darstellung, 11B-, 13C-NMR- und Schwingungsspektren von Cs2[B6Cl5(p-C6H4(NI-I2))] sowie Kristallstruktur von (Ph4P)2[B6Cl5(p-C6H4(NH2))]·2CH3CN · 0,5 Et2O / Preparation, 11B, 13C NMR and Vibrational Spectra of Cs2[B6Cl5(p-C6H4(NH2))] and Crystal Structure of (Ph4P)2[B6Cl5(p-C6H4(NH2))]· 2CH3CN · 0.5 Et2O
Authors: Zander S. , Preetz W.
Published: February 2015

By reduction of [B6Cl5(p-C6H4 (NO2))]2- with hydrazine in the presence of Raney nickel in dichlorom ethane solution the amino derivative [B6Cl5(p-C6H4(NH2)]2-is formed. X -ray diffraction analysis has been performed on a single crystal of (Ph4P)2[B6Cl5(p-C6H4(NH2] ·2CH3CN-0,5Et2O(triclinic, space group P1̅, a = 12.870(6), b = 12.9406(5), c = 35,870(7) Å , a = 91,63(4), ß = 93,22(7), γ = 98,04(8)°, Z = 2). The 11B NMR spectrum is consistent with a monosubstituted B6 cluster. The IR and R am an spectra exhibit characteristic BB, CH , CC, and NH vibrations, respectively.
Crystallographic and Spectroscopic Evidence of O-Bonding in 3d-MetaI Dicyanomethanidonitrite Complexes
Authors: Hvastijová M. , Kohout J. , Buchler J. W. , Katzenmeier H. W. , Kožíšek J. , Didierjean C.
Published: February 2015

The coordination of the dicyanomethanidonitrite group through the nitroso oxygen atom in the tetrakis(pyridine) complexes [M{ONC(CN)2}2(py)4], M = Ni, Co, Cu, and in the bis(pyridine) complex [Cu{ONC(CN)2}2(py)2] was proved by X-ray crystallography of the Ni11 complex and re-evaluated infrared spectra. The Ni11 and Co11 complexes exhibit almost octahedral structures composed of four pyridine nitrogen atoms and two oxygen atoms of dicyanomethanidonitrite ions. Both copper(II) complexes display a considerable axial distortion of the pseudooctahedral arrangement. In the bis(pyridine) Cu11 complex the ONC(CN)2 groups are involved in the bridging function by use of the oxygen and nitrile nitrogen atoms.
Rubidium- und Caesium-Oxoantimonate(V) mit Kanalstrukturen. Synthesen, Kristallstrukturen und Schwingungsspektren / Rubidium and Caesium Oxoantim onates(V) with Channel Structures. Syntheses, Crystal Structures and Vibrational Spectra
Authors: Hirschle Christian , Rosstauscher Jürgen , Emmerling Franziska , Röhr Caroline
Published: February 2015

The oxoantimonates(V) Cs2Sb4O11 (monoclinic, C2/m, a=1964.5(5), b=762.8(2), c=730.2(2) pm, β=96.276(5)°, Z=4) and A3Sb5014 (A=Rb/Cs; orthorhombic, Pbam, a=718.81 (9)/ 743.37(13), b=2447.8(2)/2625.1(5), c=733.1(2)/739.6(3) pm, Z=4) were synthesized from Sb205 and the peroxides AO2 (A=Rb, Cs). Their crystal structures were determined on the basis of single crystal diffractometer data. The structures are composed of three-dimensional nets of [SbO6 ]octahedra connected via common corners and edges, with the A cations incorporated in the resulting channel systems. The Raman spectra of the compounds are discussed in relation with the different type of oxide connectivites in the oxoantimonate anions.
Darstellung und Strukturelle Charakterisierung von cis-und trans- Dicyclohexyl-3,3′,4,4′-tetracarbonsäure-tetramethylestern / Preparation and Structural Characterization of cis- and trans-Tetramethyl Dicyclohexyl-3,3′,4,4′-tetracarboxylates
Authors: Shiotani Akinori
Published: February 2015

In the catalytic hydrogenation of tetramethyl biphenyl-3,3′,4,4′-tetracarboxylate, tetramethyl dicyclohexyl-3,3′,4,4′-tetracarboxylates were obtained, from which we have isolated cis isomers as crystals. The base-catalyzed isomerization afforded the trans isomers. The structure of the products isolated was determined by single-crystal x-ray diffraction, which clearly reveals the axial and equatorial positions of the methoxycarbonyl group. The structures in solution are supported by 1H and 13C NMR data, and also by two-dimensional COSY techniques.
Synthesis, Spectroscopic Characterization and Crystal and Molecular Structures of {Ph4P[(Se04 )(SnPh3 )(SnPh3X)]}n (X = Cl, Br)
Authors: Diop C. A. , Diop L. , Russo U. , Sánchez-Díaz A. , Castiñeiras A.
Published: February 2015

The reactions of bis[triphenyltin(IV)] selenate monohydrate [(Ph3Sn)2O4Se · H2O ] with tetraphenylphosphonium halides Ph4PX (X = Cl, Br) led to the formation of 1:1 complexes of formula {Ph4P[(SeO4)(SnPh3 (SnPh3X)]k [X = Br (I) or Cl (II)], which were characterized by infrared, Mössbauer and H, 13C and Sn 119Sn NMR techniques and by X-ray diffractometry. The complexes have polymeric structures in which the [SnPh3]+ units alternate with bridging [SeO4]2- units, each of which also bears an SnPh3X side chain. In both the [SnPh3]+ and the [SnPh3X] units the coordination polyhedron of the tin atom is a distorted trigonal bipyramid.
New Metal-Rich Compounds NblrSi, NblrGe, and TalrSi -Synthesis, Structure, and Magnetic Properties
Authors: Mishra Ratikanta , Pöttgen Rainer , Kotzyba Gunter
Published: February 2015

The metal-rich intermetallic compounds NblrSi, NblrGe, and TalrSi were synthesized by arc-melting of the elements and subsequent annealing in glassy carbon crucibles in a high-frequency furnace. The three compounds were investigated by X-ray diffraction on powders and single crystals: TiNiSi type, Pnma, a = 641.27(3), b = 379.48(2), c = 727.70(3) pm, wR2 = 0.0773, 430 F2 values for NblrSi, a = 645.48(3), b = 389.21(2), c = 741.11(4) pm, wR2 = 0.0981, 297 F2 values for NblrGe, and a = 638.11(3), b = 378.69(2), c = 726.78(3) pm, wR2 = 0.0887, 290 F2 values for TalrSi with 20 variables for each refinement. The iridium and silicon (germanium) atoms form a three-dimensional network of puckered Ir3Si3 and Ir3Ge3 hexagons in which the niobium (tantalum) atoms fill larger cages. Magnetic susceptibility measurements on NblrSi and TalrSi indicate Pauli paramagnetism with room temperature susceptibilities of 0.30(5)·10-9 and 0.97(5)·10-9 m3/mol, respectively.
Wechselwirkungen in Molekülkristallen, 175 [1, 2]. Kristallzüchtung und Strukturbestimmung von {Cäsium-tetraphenylimido- diphosphat}-Aggregaten mit unterschiedlicher lipophiler Umhüllung durch verschiedenartig Methyl-substituierte Phenylringe sowie relativistische DFT-Modellberechnungen zu Cäsium/Cäsium-Wechselwirkungen / Interaction in M olecular Crystals, 175 [1,2]. Crystal Growth and Structure Determination of {Cesium-tetraphenylimidodiphosphate} Aggregates with Differing Lipophilic Wrapping Due to Differently Methyl-Substituted Phenyl Rings, and Relativistic DFT-Model Calculations of Cesium/Cesium Interactions
Authors: Bock Hans , Heigel Erik , Havlas Zdenek
Published: February 2015

In alkali-tetraphenylimidodiphosphate ion aggregates, the size of the cation determines the curvature of the ligand and, therefore, whether hexameric ellipsoidal clusters or polymeric chains are formed. To further characterize the ligand spatial requirements, the phenyl rings have been methylsubstituted in 4-, 3/5-, 3/4- or 2,3-positions, their conformations structurally analyzed and correlated with the van der Waals substituent profiles. In addition, relativistic density functional theory potential curves have been calculated for the Cs⊕ ··· Cs⊕

interactions in simplified model systems.
Synthesis and Solid-Phase Application of a 9-Xanthenyl Handle
Authors: Somlai Csaba , Hegyes Péter , Fenyö Róbert , Tóth Gábor K. , Penke Botond , Voelter Wolfgang
Published: February 2015

The acid-labile 5-[(9-aminoxanthen-2-yl)oxy]valeric acid was prepared in a six-step route. The usefulness of the resulting handle was investigated with solid-phase peptide synthesis of cholecystokinin-8 sulfate and the phosphorylated fragment of the ζ-subunit of the T-cell receptor complex 138-144.