bluuebunny/crossref_metadata_2025 huggingface dataset:
Neuartige zwitterionische λ5-Spirosilicate: Synthese und Kristallstruktur von Bis[l,2-benzoldiolato(2 – )][2-(dimethylammonio)phenyl]silicat sowie Synthese von Bis[2,3-naphthalindiolato(2 – )][2-(dimethylammonio)phenyl]silicat-Hemiacetonitril-Solvat / Novel Zwitterionic λ5-Spirosilicates: Synthesis and Crystal Structure of Bis[1,2-benzenediolato(2–)][2-(dimethylammonio)phenyl]silicate and Synthesis of Bis[2,3-naphthalenediolato(2–)][2-(dimethylammonio)phenyl]silicate Hemiacetonitrile Solvate
Authors: Tacke Reinhold , Wiesenberger Frank , Lopez-Mras Angel , Sperlich Jörg , Mattern Günter
Published: March 2015

The zwitterionic λ5-spirosilicates bis[1,2-benzenediolato(2–)][2-(dimethylammonio)-phenyl]silicate (4) and bis [2,3-naphthalenediolato(2–)][2-(dimethylammonio)phenyl]silicate (5; isolated as 5 · ½CH3CN) were synthesized and the crystal structure of 4 was studied by X-ray diffraction. 4 was prepared by reaction of [2-(dimethylamino)phenyl]trimethoxysilane (7) or bis[2-(dimethylamino)phenyl]dimethoxysilane (8) with 1,2-dihydroxybenzene in acetonitrile at room temperature. 5 was synthesized analogously by reaction of 7 or 8 with 2,3-dihydroxynaphthalene. The silanes 7 and 8 were obtained by reaction of tetramethoxysilane (6) with [2-(dimethylamino)phenyl]lithium. The reactions 8 → 4 and 8 → 5 involve a remarkable Si–C cleavage leading to the formation of (dimethylamino)benzene. The pentacoordinate silicon atoms of 4 and 5 are surrounded by four oxygen atoms and one sp2 hybridized carbon atom. The coordination polyhedron of 4 can be described as a distorted square pyramid, the carbon atom being in the apical position (the structure is distorted by 69,1 % from the trigonal bipyramid towards the square pyramid). In the crystal, 4 forms an intramolecular N-H···O hydrogen bond.
Untersuchung zur 6-Hydroxyindol-Bildung bei der Nenitzescu-Reaktion, IV [1]. Cyclisierung von N-(Chinonylalkyl)enaminon-Derivaten, II [2] / Investigation on the Formation of 6-Hydroxyindole in the Nenitzescu Reaction, IV [1]. Cyclization of N-(Quinonylalkyl)enaminone Derivatives, II [2]
Authors: Kuckländer Uwe , Kuna Krystina , Zerta Gabriele , Poll Wolfgang
Published: March 2015

Quinonylmethylenaminones 5 and 6 are synthesized and cyclized to spiro compounds 7 and 8. Quinonylpropylenaminone 15 is made in the same way. Cyclization in acetic acid yields quinolines 11 and 12, in trifluoroacetic acid/trifluoroacetic anhydrid diacylenamine 16 is obtained. The product of 15 in perchloric acid is benzazocine 20. The structure of 20 is proven by X-ray analysis. The course of the reaction is discussed.
Übergangsmetallkomplexe mit Schwefelliganden, XC Synthese, Säure/Base- und Redoxreaktionen von [Ni(′N2H2S2′)]: auf der Suche nach Modellkomplexen für die Nickelzentren in Hydrogenasen und CO-Dehydrogenasen. (′N2H2S2′′2- = 1,2-Ethandiamin-N,N′-bis(2-benzolthiolat)(2–)) / Transition Metal Complexes with Sulfur Ligands, XC. Synthesis, Acid Base and Redox Reactions of [Ni(′N2H2S2′)]: A Search for Model Complexes for the Nickel Sites in Hydrogenases and CO-Dehydrogenases. (′Ν2Η2S2
′2- = 1,2-Ethanediamine-N,N′-bis(2-benzenethiolate)(2-))
Authors: Sellmann Dieter , Prechtel Werner , Knoch Falk , Moll Matthias
Published: March 2015

[Ni(′N2H2S2′)], 1, forms from Ni(II) salts and the tetradentate thiolate-amine ligand ′N2H2S2
′2- (= 1,2-ethanediamine-N,N′-bis(2-benzenethiolate)(2-)) [2], or by reduction of the Schiff base complex [Ni(gma)] (gma2- = glyoxal-bis(2-mercaptoanilide(2–))) with NaBH4.

Bases easily deprotonate 1 to yield the [Ni(′N2S2′)]2- dianion, which is extremely easily oxidized to give the Ni(II) monoanion [Ni(′N2S2′)]- which was isolated as [AsPh4][Ni(′N2S2′)], 4, and characterized by X-ray structure analysis. 4 contains a distorted square planar NiN2S2 core, in which two thiolate-S and two amido-N donors are surrounding the nickel atom.

Deprotonation of 1 was further substantiated by H*/D+ exchange to give [Ni(′N2D2S2′)] and by alkylation. Consecutive reaction of 1 with n-BuLi and CH3I leads to fourfold methylation of 1 yielding [Ni(′N2Me2S2Me2′)I2], 8, while alkylation of 1 by CH3I in the absence of base yields [Ni(′N2H2S2Me2′)I2], 5, in which only the thiolate donors have been alkylated. X-ray structure analysis shows 8 to contain a distorted octahedral NiN2S2I2 core with two sulfur atoms occupying axial trans positions and two nitrogen and two iodine atoms occupying equatorial cis positions. 1 also forms by reaction of [Ni(CO)4] with ′N2H2S2′-H2, which is explained by a series of oxidative addition and reductive elimination reactions.

Palladium and platinum homologues [Pd(′N2H2S2′)], 9 and [Pt(′N2H2S2′)], 10, were synthesized from [MC12(COD)] (M = Pd, Pt) and ′N2H2S2′-H2, and exhibit analogous reactivity as 1.
Photochemistry of 2-(2-Furyl)-benzimidazole (Fuberidazole)
Authors: Melo M. J. , Pina Fernando , Maçanita António L. , Melo Eurico C. , Herrmann Christiane , Förster Rolf , Koch Helmut , Wamhoff Heinrich
Published: March 2015

The photodegradation of 2-(2-Furyl)-benzimidazole (Fuberidazole 1) has been reinvestigated employing advanced HPLC—UV/VIS technique and fluorescence emission and excitation spectroscopy in methanol at natural pH, in acidic medium and in aqueous solutions at pH 7 and 3, and four main products benzimidazole-2-carboxylic acid 3, its methyl ester 2, 1-methoxy benzimidazole 5, methyl 4-oxo-2-benzimidazole crotonate 7 (cis and trans isomers) besides benzimidazole 4 and 2,2′-bibenzimidazole 6 and other side products have been isolated and characterized. The kinetics of the photodegradation process was followed independently by HPLC—UV and fluorescence emission showing a significant similarity of the curve habit; this allows to monitor a photodegradation at very low concentrations (5·10-5-5·10-6Μ). The quantum yield of disappearance of Fuberidazole has been determined.
Synthese, Kristallstruktur und 1H-NMR-Spektrum des vierkernigen Komplexes [{LTi(OCH3)}2(μ-O)4{Ti(acac)2}2](C104)2·2 H2O / Synthesis, Crystal Structure and 1H NMR Spectrum of the Tetranuclear Complex [{ LTi(OCH3)}2(μ-O)4{Ti(acac)2})2](C104)2·2 H2O
Authors: Jeske Peter , Wieghardt Karl , Nuber Bernhard
Published: March 2015

Reaction of LTiCl3 (L = 1,4,7-trimethyl-1,4,7-triazacyclononane) in CH3OH with sodium 2,4-pentanedionate (acac) in the presence of air yields upon addition of NaClO4 yellow crystals of the tetranuclear complex [{LTi(OCH3)}2(μ-O)4{Ti(acac)2}2](ClO4)2·2H2O (1), the crystal structure of which has been determined. Crystal data: monoclinic, P21/c, a = 9.563(4), b = 22.695(8), c = 13.842(5)Å, β = 93.69(3)°; Z = 2. The 400 MHz 1H NMR spectrum shows that two different isomers with Δ, Λ -configuration at the Ti(acac)2(μ-O)2- and (δδδ) or (λλλ) conformation at the LTi(OCH3)(μ-O)2-fragment cocrystallize.
Studies with Alkylheteroaromatic Carbonitriles: A Novel Synthesis of Pyrazolo[2′,3′: 3,4]benzo[c]-1,2,4-triazine
Authors: El-Ghandour Ahmed Hafez Hussein , Ibrahim Mohamed Kamal Ahmed , Abdel-Hafiz Ibrahim Saad , Elnagdi Mohamed Hilmy
Published: March 2015

A novel synthesis of derivatives of the title ring system by reacting methylpyrazolo[5,1-c]-1,2,4-triazin-6-carbonitriles (9) with sulphur and subsequent treatment of the resulting thienopyrazolotriazines with acetivated double bond system is described.
NOTIZEN: Notiz zur vierfachen HX-Eliminierung aus peri-Tetrakis(chlormethyl)-aromaten unter Blitzvakuumthermolyse: Pyracylen / Note on Fourfold HX-Elimination from peri-Tetrakis(chloromethyl)-aromatic Compounds by Flash Vacuum Pyrolysis
Authors: Dehmlow Eckehard V. , Fründ Michael
Published: March 2015

Gas phase pyrolysis in vacuo transforms 1,4,5,8-tetrakis(chloromethyl)naphthalene into pyracyclene.
Structure and Magnetic Properties of a Dinuclear, Doubly Methoxo-Bridged Iron(III) Complex with Tetrahydrosalen as Capping Ligand
Authors: Baran Peter , Böttcher Arnd , Elias Horst , Haase Wolfgang , Hüber Martina , Fuess Hartmut , Paulus Helmut
Published: March 2015

The reaction of the tetrahydrosalen ligand H2L = N,N′-bis(2-hydroxy-3-t-butyl-5-methylbenzyl)- 1,2-diaminoethane with iron(III) chloride in the presence of sodium methoxide affords a neutral complex of the composition [FeL(OMe)]. Single crystal X-ray analysis of this complex shows dinuclear units, [FeL(OMe)]2 = 1, with two methoxide bridges. Complex 1 crystallizes in the monoclinic space group C 2/c with a = 31.67(1)Å, b = 12.544(4)Å, c = 14.135(5)Å and β = 101.33(1)°. The two edge-sharing FeO4N2-octahedra are distorted and connected by a center of inversion. The iron(III) centers are separated by 3.203 Å and weakly antiferromagnetically coupled (J = —5.7 cm-1), which follows from temperature-dependent magnetic susceptibility measurements in the range 4.2 to 280 K. The effective magnetic moment per iron(III) is µeff = 5.24 μΒ at 280 K. The observed small coupling constant J fits well into the magnetostructural relationship suggested recently by Gorun and Lippard (Inorg. Chem. 30,1625 (1991)).
Synthese und Reaktivität eines Azavinyliden(hydrido)osmium-Komplexes / Synthesis and Reactivity of a Azavinylidene(hydrido)osmium Complex
Authors: Daniel Thomas , Werner Helmut
Published: March 2015

The azavinylidene osmium complex [OsH(=N=CPh2)(CO)(PiPr3)2] (2) is prepared either from [OsHCl(CO)(PiPr3)2] (1) and MN=CPh2 (M = Li, Na) or from [OsHCl(NH=CPh2)(CO)(PiPr3)2] (3) by HCl elimination with ΚΟ-t-Bu. The IR and NMR spectroscopic data of 2 provide evidence that a linear Os—N—C unit is present. Complex 2 reacts with CH3OH to give the isomeric ortho-metallated compound [OsH{NH=C(Ph)C6H4}(CO)(PiPr3)2] (5). With CD3OD instead of CH3OH, the mono-deuterated derivative [OsH{ND=C(Ph)C6H4}(CO)(PiPr3)2] (5-d1) is obtained.
Dinuclear Gold(I) Chloride Complexes of 1,4-Bis(diphenylphosphinyl)butane and 1,5-Bis(diphenylphosphinyl)pentane: A Conformational Study
Authors: Schmidbaur H. , Bissinger P. , Lachmann J. , Steigelmann O.
Published: March 2015

[1,4-Bis(diphenylphosphinyl)butane]digold dichloride 1 and [1,5-bis(diphenylphosphinyl)-pentane]digold dichloride 2 have been prepared from R2SAuCl (R = CH2CH2OH) and the corresponding bidentate phosphines Ph2P(CH2)nPPh2 (n = 4 or 5) in good yields. The structures of the compounds have been determined by single crystal X-ray diffraction (1 · CH2C12: space group P1̅, Z = 2; 2·0.5 CH2Cl2: space group C 2/c, Z = 8). While the monomers [Ph2P(CH2)5PPh2] (AuCl)2 are associated through intermolecular Au···Au contacts (3.323 Å) to form a chain-like structure, the crystal lattice of 1· CH2Cl2 features independent [Ph2P(CH2)4PPh2](AuCl)2 molecules which show no intra- or intermolecular Au···Au interactions. This exceptional behaviour can be rationalized on the basis of efficient packing of solvent molecules and molecules 1 with a particularly favourable conformation, which cannot be altered by weak Au(d10)—Au(d10) interactions.
Some Aspects of the Molecular Surface of Sandalwood Odour Molecules. Conformational Calculations on Sandalwood Odour VII
Authors: Buchbauer Gerhard , Stock Alexander , Weiß Petra , Winiwarter Susanne , Wolschann Peter
Published: March 2015

The molecular surfaces of five different sandalwood odour molecules were investigated and subsequently used as a basis for a mean surface and compared to each other. It was possible to find a specific surface part with a significant pattern, which seems to be necessary for evoking the typical odour.
Synthese von N-[(3-Ethoxycarbonylmethyl)-cyclohexyl]-azetidin-2-ylpropansäurehydrochlorid / Synthesis of N-[(3-Ethoxycarbonylmethyl)-cyclohexyl]-azetidin-2-yl-propionic Acid Hydrochloride
Authors: Habermehl Gerhard G. , Wilhelm Jörg-Hubertus
Published: March 2015

In order to find a new synthesis of gephyrotoxin 1 an alkaloid from the neotropical poison frog Dendrobatidae the compounds 3 and 4 were synthesized. However they reacted not to the decahydroquinoline derivative 2 but to the title compound 5.
Notizen: Darstellung und Eigenschaften von und Reaktionen mit metallhaltigen Heterocyclen, LXXXI Synthese und Kristallstruktur eines Phospha-arsa-mangana-cyclopropans / Metal-Containing Heterocycles: Preparation, Properties, and Reactions, LXXXI Synthesis and Crystal Structure of a Phospha-arsa-mangana-cyclopropane
Authors: Lindner Ekkehard , Fisahn Paul , Fawzi Riad , Steimann Manfred
Published: March 2015

The phospha-arsa-mangana-cyclopropane (OC)4Mn–PPh2–AsAr (4) [Ar = 2,4,6-(t-Bu)3C6H2] is obtained in a one-pot reaction proceeding in the sequence Mn2(CO)10 → HMn(CO)5 (1) → HMn(CO)4PPh2H (2) → Li2[(OC)4Mn—⃛PPh2] (3) → 4. According to an X-ray structural analysis 4 has a short P–As bond (229 pm) and a long Mn–As distance (262 pm).
Notizen: Naturstoffchemie, 155. Mitteilung. Eine einfache Synthese von 4-(Herniarin-3-yl)-2-methyl-3-buten-2-ol / Chemistry of Natural Products, Part 155. A Simple Synthesis of 4-(Herniarine-3-yl)-2-methyl-3-buten-2-ol
Authors: Reisch Johannes , Zappel Johannes
Published: March 2015

A simple synthesis of 4-(herniarine-3-yl)-2-methyl-3-buten-2-ol from umbelliferone in relatively high yield is described.
Notizen: Vereinfachter Zugang zu 5-Acetyltetrazol / An Expedient Synthesis of 5-Acetyltetrazole
Authors: Moderhack Dietrich , Beißner Andreas
Published: March 2015

5-Acetyltetrazole can be obtained in 75% yield by reacting 5-tetrazolecarbonitrile (the latter available by an efficient literature procedure) with an excess of methylmagnesium iodide.
Synthesis of N-Silylated Diaminosulfanes from Functionally Substituted Sulfur Diimides and Hexachlorodisilane and Octachlorotrisilane-Multinuclear Magnetic Resonance Studies and X-Ray Structure Determination of a Non-Cyclic Diaminosulfane
Authors: Herberhold Max , Gerstmann Silke , Milius Wolfgang , Wrackmeyer Bernd
Published: March 2015

Sulfur diimides R1(NSN)R2 (1) with different substituents R1 and/or R2 or with functional groups react with hexachlorodisilane (2) or octachlorotrisilane (3) to give the corresponding diaminosulfanes (4, 5) in quantitative yield. The formation of cyclic intermediates prior to the redox process is discussed. The products have been characterized by 1H, 13C, 15N and 29Si NMR in solution as well as by 15N and 29Si CP/MAS NMR in the solid state (4a, 4f). The crystal structure of ClMe2Si(Cl3Si)NSN(SiCl3)SiMe2Cl (4f) has been determined: space group PĪ (no. 2) with a = 864.2(2), b = 1096.8(2), c = 1232.7(2) pm and Z = 2.
Synthesis, Structure and Characterization of Trisodium Bis[N-(2-oximinopropionyl)glycinato(3 – )-O,N,N'] Cobaltate(III) Nonahydrate
Authors: Fritsky Igor O. , Lampeka Rostislav D. , Skopenko Victor V. , Simonov Yury A. , Dvorkin Alexander A. , Malinowsky Tadeusz I.
Published: March 2015

A cobalt(III) complex with pyruvylglycine oxime (H3G) of composition Na3[CoG2] · 9 H2O is synthesized and investigated by means of X-ray analysis, infrared, electronic and NMR spectroscopy. The crystals are triclinic, space group P1̄, a = 15.477(5), b = 9.931(4), c = 7.773(4)Å; α = 75.60(3); β = 82.86(4); γ = 93.54(3)°; Ζ = 2. The structure was refined to final R = 0.036 for 3347 independent observed reflections. The structure consists of the complex anions, Na+ cations and water molecules. The ligands are coordinated via the deprotonated oxime and amide nitrogen and the carboxyl oxygen atoms in a meridional fashion (Co—O(carboxyl) = 1.971 and 1.947 Å; Co— N(oxime) = 1.891 and 1.909; Co— N(amide) = 1.876 and 1.866Å). The Co(III) coordination octahedron is slightly distorted; the Co—O and Co—N distances are in agreement with the data for oxime and peptide complexes of Co(III). The unit cell contains 2 enantiomeric complex anions related by a center of symmetry. The electronic, IR and NMR (1H and 13C) spectra of the complex are compared to those of the free ligand and of dipeptidato complexes of Co(III).
Neue metallorganisch substituierte Zinn-Chalkogen-Heterocyclen. Synthese und Kristallstrukturen von [ { (CO)4Co }4Sn2E2] (E = S, Se) / New Organometallic Tin Chalcogen Heterocycles. Synthesis and Crystal Structures of [{(CO)4Co}4Sn2E2] (E = S, Se)
Authors: Merzweiler Kurt , Kraus Harald , Weisse Laurent
Published: March 2015

[{(CO)4Co}2SnCl2] reacts with silylated chalcogens E(SiMe3)2 (E = S, Se) to form the compounds [{(CO)4Co}4Sn2E2] (E = S (1), Se (2)). According to crystal structure determinations 1 and 2 contain planar Sn2E2 rings. The Sn atoms are coordinated nearly tetrahedrally by two bridging chalcogen atoms and two {(CO)4Co} groups.
Synthese, Struktur und Eigenschaften von kubanartigen Molybdän-Kupfer-Schwefel-Cluster-Dithiophosphinaten / Synthesis, Structure, and Properties of Cubane-Type Molybdenum-Copper-Sulfur Cluster Dithiophosphinates
Authors: Diller Hansjörg , Keck Helmut , Kuchen Wilhelm , Mootz Dietrich , Wiskemann René
Published: March 2015

The diamagnetic tetranuclear cluster complexes Mo3CuS4I(R2PS2)4•C5H5N 2 (a: R=Et, b: R=Pr) are obtained by reaction of Mo3S4L4 (L = R2PS2-) 1 with CuI and pyridine. Each Mo atom of the cubane-type Mo3CuS4 core is chelated by L. Two of the Mo atoms are bridged by the fourth L, while a pyridine ligand completes the coordination sphere of the third Mo atom, and iodine is bonded to the Cu atom. Magnetic, NMR- and MS-spectroscopic data are given. 2b crystallizes in the monoclinic space group P21/n with Z = 4 and lattice parameters a = 21,164(7), b = 10,653(3), c = 25,455(8)Å, and β = 106,25(3)°.
Organophosphorverbindungen mit tertiären Alkylsubstituenten, II*: Synthese und Charakterisierung triphenylmethylsubstituierter λ4P(V)-Verbindungen; Kristallstruktur von Triphenylmethyl-Phosphonsäuredifluorid / Organophosphorus Compounds with Tertiary Alkyl Substituents, II*:
Synthesis and Characterization of Triphenylmethyl-Substituted λ4P(V) Compounds;
Crystal Structure of Triphenylmethylphosphonic Difluoride
Authors: Goerlich Jens R. , Fischer Axel , Jones Peter G. , Plack Volker , Schmutzler Reinhard
Published: March 2015

The synthesis of the triphenylmethyl-phosphonic and -phosphonothioic dihalides Ph3CP(:X)Y2 (X = O, S; Y = F, Cl) is described. The NMR parameters of these compounds are discussed and compared to these of other phosphonic and thiophosphonic dihalides. Single crystal X-ray analysis was used to confirm the structure of Ph3CP(:O)F2 2 [C2/c, a = 1599.6(4), b = 1096.3(3), c = 1863.1(7) pm, ß = 109.11(2)°, T = 178 K, R = 0.034]. The geometry at the phosphorus atom is approximately tetrahedral. The bonds between phosphorus and fluorine are extremely short [P— F 153.1(1) and 153.3(1) pm]. Bond distances and angles for this compound are compared to those of methylphosphonic difluoride which were obtained from microwave spectra.
Spectroscopic and X-Ray Investigation of Cobalt(III) Complexes with 2-Oximinocarboxylic Acids
Authors: Lampeka Rostislav D. , Uzakbergenova Zamira D. , Skopenko Victor V.
Published: March 2015

Mixed complexes of Co(III) with 2-oximinopropionic (H2A) or 2-oximino-3-phenylpropionic (H2B) acid and different amine (imidazole, benzimidazole, pyridine, β-picoline, γ-picoline) are reported. Characterization of the complexes was based upon elemental analysis, conductivity and JR, 1H NMR, and electronic absorption spectra, and X-ray diffraction analysis. The organic ligands behave as O,N donors via the carboxyl oxygen and the oxime nitrogen atoms. A trans-octahedral structure has been assigned to the bis(2-oximinocarboxylato)bis(amine)cobalt(III) on the basis of 1H NMR data.

The crystal and molecular structures of the complexes trans-[bis(2-oximinopropionato)bis-(imidazole)]- (I) and trans-[bis(2-oximinopropionato)bis(pyridine)]cobalt(III) (II) were determined. I crystallizes in space group P2/n with a = 14.1 67(2), b = 8.774(1), c = 14.785(2) Å,β = 113.37(1)°, Z = 4, Dcalc = 1.568 g · cm-3. II crystallizes in space group P1̄ with a = 9.122(2), b = 10.038(2), c = 11.759(2) Å, α = 69.95(1)°, β = 67.47(2)°, γ = 69.49(2)°, Ζ = 2, Dcalc = 1.547 g cm-3. The structures were refined to unweighted R factors of 0.036 and 0.028, respectively. The coordination sphere around Co is pseudo-octahedral with the 2-oximinopropionato ligands occupying four equatorial positions, and the amines in axial positions.
Electrochemistry of Oxygenation Catalysts, Part 2+ Improved Synthesis, Crystal Structure, and Electrochemical Properties of N,N′-Bis(salicylidene)ethylenediaminatocobalt(III) Chloride
Authors: Eichhorn Emerich , Rieker Anton , Speiser Bernd , Sieglen Jürgen , Strähle Joachim
Published: March 2015

N,N′-Bis(salicylidene)ethylenediaminatocobalt(III) hydroxide is treated with chloroform in methanol to yield the corresponding chloride in pure, crystalline form. Results of the crystal structure determination compare well with those in earlier reports of dimeric [Co(salen)Cl]2 units and incorporated CHCl3 molecules. Electrochemical experiments in DMF and pyridine show that the chloride fully dissociates in these donor solvents. Thus, the quasireversible oneelectron reduction to Co(salen) is observed in cyclic voltammograms.
Electrochemical Synthesis of N-Oxopyridine-2-thionate Complexes of Cd(II): The Crystal Structure of Bis(2,2′-bipyridine)(N-oxopyridine-2-thionate) Cadmium(II) Perchlorate 1/4 (Bipyridine)
Authors: Sanmartin J. , Bermejo M. R. , Romero J. , García-Váquez J. A. , Sousa A. , Brodbeck A. , Castiñeiras A. , Hiller W. , Strähle J.
Published: March 2015

The electrochemical oxidation of Cd in acetonitrile solution of 1-hydroxy-2-pyridinethione (HPT) and 2,2′-bipyridine (bipy) affords [Cd(PT)2(bipy)] · H2O and [Cd(PT)(bipy)2]ClO4· 1/4(bipy). The crystal structure of the perchlorate salt shows the molecule to have a distorted octahedral CdN4OS skeleton.
Zur Chemie der 4,6-Dioxo-1,3,5,2-triazaphosphinane, Teil III. Darstellung von 4,6-Dioxo-1,3,5,2 λ3-, 4,6-Dioxo-1,3,5,2 λ4- und 4,6-Dioxo-1,3,5,2 λ5-triazaphosphinanen / Chemistry of the 4,6-Dioxo-1,3,5,2 λ3-triazaphosphinanes, Part III. Synthesis of 4,6-Dioxo-1,3,5,2 λ3-, 4,6-Dioxo-1,3,5,2 λ4-, and 4,6-Dioxo- 1,3,5,2 λ5-triazaphosphinanes
Authors: Neda Ion , Farkens Michael , Fischer Axel , Jones Peter G. , Schmutzler Reinhard
Published: March 2015

In the reaction of 2-chloro-1,3,5-trimethyl-4,6-dioxo-1,3,5,2 λ3-triazaphosphinane (1) with β-chloroethylamine hydrochloride and bis-(β-chloroethyl)amine hydrochloride, 1,3,5-trimethyl-2-(β-chloroethyl)amino-4,6-dioxo-1,3,5,2 λ3-triazaphosphinane (4) and 1,3,5-trimethyl-2-bis-(β-chloroethyl)amino-4,6-dioxo-1,3,5,2 λ3-triazaphosphinane (5) were obtained. The reaction of 4 and 5 with sulfur, hexafluoroacetone, tetrachloroorthobenzoquinone and 4-nitrobenzoyl azide gave the 1,3,5-trimethy1-4,6-dioxo-1,3,5,2 λ4-triazaphosphinanes 6 and 9 and the 1,3,5-trimethyl-4,6-dioxo-1,3,5,2 λ5-triazaphosphinanes 7 and 8. The characterization of 4-9 rests, especially, on their 1H, 13C and 31P NMR spectra, mass spectra and X-ray structure determinations of 4 and 5.
Verbesserte präparative Darstellung von Polyisopropyl- und Poly-tert-butylcyclopentadienen / Improved Preparation of Polyisopropyl- and -tert-butylcyclopentadienes
Authors: Dehmlow Eckehard V. , Bollmann Christof
Published: March 2015

Phase transfer catalytic isopropylation or tert-butylation of cyclopentadiene yields 1-6 in efficient one-pot procedures. Powdered potassium hydroxide or solid sodium hydride are the prefered bases, Aliquat 336 or dibenzo-18-crown-6 are the PT catalysts.
Two Bioactive Linear Diterpene Diols from the Sponge Myrmekwdevma styx
Authors: Albrizio Stefania , Ciminiello Patrizia , Fattorusso Ernesto , Magno Silvana , Ialenti Armando , Rosa Massimo Di
Published: March 2015

Two linear dihydroxy diterpenes were isolated from the sponge Myrmekioderma styx. The structure of these com pounds were deduced by MS, UV, IR , 1H and 13C NMR , 1H - 1H COSY , XHCORR , and COLOC experiments. Both com pounds 5 and 6 are toxic toward Artemia salina; compound 5 showed inflammatory activity, by histamine release.
Reaktionen von Derivaten der (Diphenylmethylen-amino)-essigsäure mit Schwefelkohlenstoff und Phenylisothiocyanat sowie Kristall- und Molekülstruktur des 2-(Diphenylmethylen-amino)-2-(1,3-dithian-2-yliden)-essigsäuremethylesters / Reactions of the Derivatives of (Diphenylmethylene-amino) Acetic Acid with Carbon Disulfide and Phenyl Isothiocyanate and Crystal and Molecular Structure of Methyl 2-(Diphenylmethylene-amino)-2-(1,3-dithiane-2-ylidene) Acetate
Authors: Dölling Wolfgang , Frost Klaus , Heinemann Frank , Hartung Helmut
Published: March 2015

Derivatives of (diphenylmethylene-amino) acetic acid 1-3 react in the presence of bases (NaH, t-BuONa) or under phase transfer conditions with carbon disulfide to give the corresponding ketene dithioacetals 4-11 after alkylation. Phenyl isothiocyanate and dicyclohexyl carbodiimide give rise to ketene-S,N- and N,N-acetals. Methyl 2-(diphenylmethyleneamino)-2-(1,3-dithiane-2-ylidene) acetate (7) was characterized by an X-ray structure determination. The compound has a 2-aza-1,3-butadiene fragment containing two well localized double bonds. The C=N-C=C group is significantly non-planar, the relevant torsion angle amounts to -103.5(3)°.
Synthesis of a Dihydroxy-Substituted Aminoxyl Spin Label and its Crown Ether and Cyclic Diester Derivatives
Authors: Zhang Yong-Kang , Shen De-Kang
Published: March 2015

A novel dihydroxy-substituted aminoxyl spin label, 4-hydroxy-3-(3'-hydroxypropyl)-2,2,6,6-tetramethylpiperidine-1-oxy (5), has been prepared. From this aminoxyl radical, a spin-labeled crown ether, 16,16,18,18-tetramethyl-2,5,8,11-tetraoxa-17-azabicyclo[ 13,4,0]-nonadecane-17-oxy (12), and a spin-labeled cyclic diester, 16,16,18,18-tetramethyl-3,10-dioxo-2,5,8,11-tetraoxa-17-azabicyclo[13,4,o]nonadecane-17-oxy (13), have been acquired. Other four new stable aminoxyl radicals 8,9,10, and 11 have also been obtained within the synthetic approach. It has been demonstrated that the cyclic ether compound (7) is generated by the reduction of its corresponding lactone which is sidely derived from the oxo-reduced species of 3 by intramolecular cyclization.
Na2TiOS2 — Ein Oxothiotitanat(IV) mit unendlichen Tetraederketten / Na2TiOS2 — An Oxothiotitanate(IV) with Infinite Tetrahedral Chains
Authors: Klepp O.
Published: March 2015

Colourless single crystals of Na2TiOS2 were obtained by a fusion reaction of a stoichiometric mixture of Na2S, Na2SO3, titanium-powder and elemental sulphur. Na2TiOS2 is monoclinic, space group P21/c with a = 6.861(3), b = 13.610(9), c = 5.733(9) Å, β = 113.24(2)°, Ζ = 4. The crystal structure (R = 0.032, 811 observations, 55 variables) is characterized by infinite anionic chains of TiO2S2-tetrahedra sharing the oxygen atoms (d̄Ti-o = 1.842 Å, d̄Ti-s = 2.227 Å,

Ti—O—Ti = 134.3°). The chains are separated from each other by octahedrally coordinated Na+ ions. The structure may be considered as a quaternary variant of the Na2GeS3-structure type.
Clusterdithiophosphinate mit kubanartigem Mo2M2S4-Kern (M = Co, W) / Clusterdithiophosphinates with Cubane-Type Mo2M2S4-Core (M = Co, W)
Authors: Diller Hansjörg , Keck Helmut , Kruse Andreas , Kuchen Wilhelm
Published: March 2015

The syntheses of tetranuclear complexes Mo,W2S4L6 3 and Mo2Co2S4L2(CO)2(CH3CN)2 4 (L = R2PS2⁻; a: R = Et, b: R = Pr) containing the cubane-type Mo2M2S4 core are reported. While in 4 both Mo atoms are chelated by L, the dithiophosphinato group acts as a chelating and bridging ligand in 3. It is shown that there exist four isomers of 3 which differ not only in the function of L but also in the kind of metals which are chelated and bridged. Magnetic and NMR spectroscopic data are given. The structure of a mixed crystal of the two β-isomers of 3a containing three bridging and three chelating ligands L is reported: orthorhombic space group Pbca, Z = 8, and lattice parameters a = 2186.6(7), b = 2264.0(7), and c = 2386.7(6) pm.
X-Ray Structural Analysis and Vibrational Spectra of Sodium Cysteine-S-sulfonate, +H3NCH(COO-)CH2S2O3Na • 3/2H2O [1]
Authors: Steudel Ralf , Albertsen Angela , Kustos Monika , Pickardt Joachim
Published: March 2015

The title compound crystallizes orthorhombically (space group C 2221) with a = 797.0, b = 870.3 and c = 2739.0 pm. The anions are zwitterions which are heavily involved in intra- and intermolecular NH •••O and OH•••O hydrogen bonding. The two types of sodium cations are coordinated by six oxygen atoms each of which belongs to either SO3 groups (Na 2) or water molecules and SO3 groups (Na1). A second type of water molecules is not coordinated to the cations. The SS bond length is 208.2 pm. Infrared and Raman spectra of the title compound are reported and tentatively assigned. The SS stretching vibration is observed at 409 cm-1.
Oligophosphan-Liganden, XXXVIII / Oligophosphine Ligands, XXXVIII
Authors: Becker Corinna , Dahlenburg Lutz , Kerstan Sabine
Published: March 2015

Intermolecular activation of carbon-hydrogen bonds has been accomplished by reduction with sodium amalgam of (sip3)(Me3P)RuCl2, 1, [“sip3” = MeSi(CH2PMe)2)3] in aromatic hydrocarbons, such as benzene and substituted derivatives thereof. In these reactions, the 16e equivalent (sip3XMe3P)Ru(O) thus generated exhibits a preference for insertion across the unhindered metaand para-C-H bonds to produce complexes of composition (sip3)(Me3P)RuH(C6H3RR′) [R = R′ = H, 2; R = H, R′ = CH3, 3; R = R′ = CH3 (3,4-xylyl), 4; R = R′ = CH3 (3,5-xylyl), 5; R = H, R′ = CF3, 6], of which 3, 4, and 6 were isolated as mixtures of meta/para-isomers and Ru-aryl rotamers, respectively. Reaction of the phenyl hydride 2 with 4-MeC6H4NCE (E = O, S) leads to insertion of the heteroallenes into the Ru-Η bond to give (sip3)(Me3P)Ru[N(C6H4Me-4)C(O)H]C6H5, 8, and (sip3)(Me3P)Ru[SC(=NC6H4Me-4)H]C6H5, 10, as the primary products. While the latter forms (sip3)

, 11, by loss of PMe3, the former reacts with another molecule of isocyanate to afford the acyl compound (sip3)

9, as the ultimate product. Treatment of 2 with CO2 results in the formation of a carbonato derivative, (sip3)(Me3P)Ru(O2CO), 7.

•
Syntheses and Structures of Three Mononuclear Coordination Compounds Containing Six- and Seven-Coordinated Manganese(II) Ions
Authors: Andruh Marius , Hübner Kay , Noltemeyer Mathias , Roesky Herbert W.
Published: March 2015

The reactions of Mn(CF3COO)2 (1) with Ν,Ν,N′,N′-tetramethylethylenediamine (tmen), 2,2′-bipyridine (bipy) and triethanolamine (tea) yield three new mononuclear coordination compounds: trans-[Mn(tmen)2(CF3COO)2] (2), cis-[Mn(bipy)2(CF3COO)2] (3), and [Mn(tea)2](CF3COO)2 (4). The X-ray structures of the compounds 2, 3, and 4 are described. The seven-coordination of the manganese(II) ion in 4, as well as the inequivalency of the two tea molecules coordinated to Mn(II) make this compound unique.
Darstellung und Eigenschaften von CH3C(CH2PPh2)3MoCl3 / Characterization and Properties of CH3C(CH2PPh2)3MoCl3
Authors: Walter Olaf , Huttner Gottfried , Zsolnai Laszlo
Published: March 2015

Starting from MoCl5 via the intermediates (MeCN)2MoCl4 (1) and (THF)2MoCl4 (2) the tripod complex CH3C(CH2PPh2)3MoCl3 (4) has been synthesized. The yellow cristalline compound 4 has been fully characterized by standard analytical techniques. X-ray-analysis proves the facial coordination of the tripod ligand. To our knowledge 4 is the first Mo(III)-trihalide coordination compound containing three P-donor-ligands in a facial coordination.
Mikro-Raman-spektroskopische Charakterisierung von CuInSe2-Dünnfilm-Halbleitern / Micro Raman Spectroscopy of CuInSe2 Thin Films
Authors: Fritz H. P. , Pöll E.
Published: March 2015

Structural properties for Cu—In—Se thin-films for solar cell applications formed by electrochemical deposition at room temperature were studied using Raman-scattering. Reactions among Cu, In and Se to binary compounds and CuInSe2, respectively, were observed. It is concluded that Raman scattering spectroscopy only at low temperature conditions shows the real composition of the electrochemically deposited Cu—In—Se layer. It was also found by Raman spectroscopy that the CuInSe, phase is formed by annealing as-deposited Cu—In—Se thin films preferentially at temperatures around 400°C under selenium vapour pressure.
Übergangsmetallkomplexe mit Schwefelliganden, XCVIII / Transition Metal Complexes with Sulfur Ligands, XCVIII
Authors: Sellmann Dieter , Ruf Richard
Published: March 2015

Depending on the H+ concentration and solvent, reaction of [RuCl3(NO)(PPh3)2] with 'S2N2H2
′2-- alternatively yields either [Ru(NO)PPh3(′S2N2H2′)]Cl 1 or [Ru(NO)(′S2N2H′)]2 2. 1 gives 2 upon treatment with base, 2 yields 1 when reacted with HC1 and PPh3 in THF. In MeOH, 2 is completely insoluble, but reacts with HC1 to give [Ru(NO)(′S2N2H2′)]2Cl2, 4a, which is converted into [RuCl(NO)(′S2N2H2′)] 3 when dissolved in THF.

Reactions of 2 with phosphines such as PMe3, PPr3 or PBu3 in THF yield the corresponding [Ru(NO)PR3(′S2N2H′)] complexes, which is proof that not a protonation of the amido donor in 2, but sufficient solubility of 2 in the respective solvent and a subsequent dissociation into mononuclear complex fragments are decisive for cleavage of 2. Protonation or deprotonation of the N donors are more likely to influence the fine-tuning of the Ru center in [Ru(NO)(′S2N2H2′)] fragments with respect to coordination of hard or soft co-ligands.
Präparation und Kristallstrukturen von Rb8In11, K8Tl11 und Rb8Tl11sowie Bandstrukturrechnungen zu K8In11 / Preparation and Crystal Structures of Rb8In11, K8Tl11, and Rb8Tl11 Band Structure Calculations on K8In11
Authors: Blase Wolfgang , Cordier Gerhard , Müller Volker , Häußermann Ulrich , Nesper Reinhard , Somer Mehmet
Published: March 2015

The isotypic compounds K8In11, Rb8In11, K8Tl11, and Rb8Tl11 were prepared from the elements. The crystal structures were determined by single crystal X-ray diffraction methods. (K8In11: a = 1002.1(3), c = 5089.1(8) pm; Rb8In11: a = 1030.1(3), c = 5236.7(7) pm; Κ8Τl11: a = 999.1(3), c = 5084.8(7) pm; Rb8Tl11: a = 1028.0(3), c = 5230.5(7) pm, R3̄c, Z = 6). The crystal structures contain In11- and Tl11-clusters, respectively, of pentacapped trigonal prisms. Band structure calculations on K8In11 confirm an [In11]7-“anion”, with one excess electron per In11-cluster involved in alkalimetal-earthmetal bonding.
Molecular Structure of the Copper(II) Complex of 20-Methoxy-mesoporphyrin IX Dimethyl Ester – A Model for the Enol-Form of Oxophlorins
Authors: Senge Mathias O. , Smith Kevin M.
Published: March 2015

The crystal structure of the title compound was determined to obtain structural information on asymmetric tetrapyrroles bearing an sp3-hybridized meso-oxygen atom. These types of compounds serve as models for the enol-form of oxophlorins, which often are obtained in crystalline form only with rotational disordering of the oxofunction, making conformational analyses difficult. C37H42CuN4O5, monoclinic, P21/n, a = 15.025(7), b = 9.204(3), c = 23.544(9) Å, β = 94.33(4)°, V = 3246.7(13) Å3, 130 K, Z = 4, R = 0.075 for 3186 reflections with I > 2.0 σ(I). The structure is characterized by a planar tetracoordinated copper(II) and an almost planar macrocycle.
Liquid Crystalline Compounds in the Thiophene Series, Part 6+ Synthesis and Characterization of Azomethines and Vinylenes with Two Mesogenic Groups and Different Alkylene Spacer Lengths
Authors: Koßmehl Gerhard , Hoppe Frank Dirk , Hirsch Barbara
Published: March 2015

Compounds which have two mesogenic groups with and without terminal alkyl chains containing thiophene systems, were prepared from α.ω-bis(5-formyl-2-thienyl)alkanes (3a-3n) and various aromatic amines or 2-fluorenyl-Wittig-salt (10). The liquid crystalline properties of these compounds were characterized by differential scanning calorimetry (DSC) and polarizing microscopy. Only the series of α.ω-bis{5-[N-(4′-butyloxybiphenyl-4-yl)imino]formyl-2-thienyl}alkanes (7a-71) showed enantiotropic smectic and nematic mesophases. The series of E,E-α.ω-bis[5-(2-fluorenylvinyl)-2-thienyl]alkanes (8a-81) showed enantiotropic nematic mesophases for the compounds with 4 and 6 methylene groups, monotropic nematic mesophases for the compounds with 7—12 methylene groups and no liquid crystalline phases for compounds with 3, 5, 16 methylene groups in the connecting alkylene chain. In contrast to the compounds 8a-81, E-l-(5-butyl-2-thienyl)-2-(2-fluorenyl)ethylene has a smectic mesophase.
Notizen: Synthesis of Novel Hydroxy-Substituted Aromatic Aminoxyl Esters and their Azo Derivatives
Authors: Zhang Yong-Kang , Shen De-Kang
Published: March 2015

Transesterification or acylation method has been used for the preparation of three novel hydroxy-substituted aromatic aminoxyl esters 4, 5, and 8 from which three new spin-labelled azo compounds 10,13, and 14 have been synthesized.
CsPr2(CH3COO)7, ein caesiumarmes wasserfreies ternäres Caesium-Praseodym-Acetat / CsPr2(CH3COO)7, a Cesium Poor Anhydrous Ternary Cesium Praseodymium(III) Acetate
Authors: Lossin Adalbert , Meyer Gerd
Published: March 2015

Single crystals of CsPr2(CH3COO)7 were obtained from an acetic acid solution of Pr(CH3COO)3 • H2O and Cs2CO3 in a molar ratio of 4:1 at 120°C. It crystallizes in the triclinic system, PĪ (no. 2), Z = 2, a = 1028.1(5), b = 1034.6(5), c = 1199.4(6) pm, α = 84.82(2), β = 67.07(3), γ = 76.01(2)°, Vm = 343.3(3) cm3/mol, R = 0.031, Rw = 0.027. The crystal structure contains infinite chains, 1
∞[Pr2(CH3COO)6], running along the [110] direction. The chains are built up by bridging acetate ions coordinated to two crystallographically different Pr3+ ions which are both surrounded by 9 oxygen ligands. These chains are linked by “intercalated” Cs(CH3COO) to layers parallel (100). Cs+ has contacts to oxygen atoms of neighbouring layers, such that a three-dimensional network is formed.
Polysulfonylamine, XLIV Synthese von [Na(15-Krone-5)][N(SO2CH3)2] und Kristallstruktur bei –95°C / Polysulfonylamines, XLIV Synthesis of [Na(15-Crown-5)][N(SO2CH3)2] and Crystal Structure at –95°C
Authors: Blaschette Armand , Nagel Karl-Heinz , Jones Peter G.
Published: March 2015

The complex [Na(15-crown-5)][N(SO2CH3)2] crystallizes at —25°C from a methanol solution containing equimolar amounts of NaN(SO2CH3)2 and 15-crown-S. Its crystallographic data at —95°C are: monoclinic, space group P 21/c, a = 852.1(5), b = 2731.9(12), c = 909.2(4) pm, β = 115.53(4)°, V = 1.910 nm3, Z = 4, Dx = 1.445 Mgm3. The structure in the solid state consists of ion pairs. The sodium cation is coordinated to the five oxygen atoms of the crown ether, one oxygen atom of the anion, and to the nitrogen atom of the anion. The bond distances are Na—O(crown) 238.7-247.2, Na—O(sulfonyl) 234.9, Na—N 275.8 pm. The sodium ion lies 78 pm out of the plane of the crown ether oxygen atoms. The conformation of the coronand is described.
Oxothiatriazine (NSCl)n(NS(Ο)Cl)3-n (n = 1,2)
Authors: Chen Shan-Jia , Behrens Ulrich , Mews Rüdiger
Published: March 2015

A modified method for the preparation of (ClSN)2(ClS(O)N) (1) and (ClSN)(ClS(O)N)2 (2) as well as the crystal structures of 1 and 2 are reported.
Neue Synthesen mit Magnesiumhydrid Teil 1: Hydromagnesierung von α-Olefinen zu Dialkylmagnesiumverbindungen / New Syntheses with Magnesium Hydride Part 1: Hydromagnesiation of α-Olefines to Magnesium-dialkyls
Authors: Knott Wilfried , Klein Klaus-Dieter
Published: March 2015

The addition of highly active magnesium hydride to α-olefines, hydromagnesiation, is a well known reaction.

The use of cheap magnesium hydride exhibiting a lower reactivity is highly desirable for industrial purposes.

In a combination of chemical and mechanical activation the low reactivity of high temperature magnesium hydride could be overcome thereby making a broad variety of magnesium alkyls accessible.
Crystal and Molecular Structures of the Sulfur-Rich Organic Polysulfanes Heptathiacyclononane (C2H4S7) and Bis(triphenylmethyl)pentaand hexasulfane
Authors: Kustos Monika , Pickardt Joachim , Albertsen Jörg , Steudel Ralf
Published: March 2015

Determination of the first structure of a chain-like polysulfane with five sulfur atoms in the chain has been attempted. Bis(triphenylmethyl)pentasulfane forms monoclinic crystals containing disordered solvent molecules preventing an accurate solution of the structure. The (Ph3C)2S5 molecules consist of a helical C–S–S–S–S–S–C backbone (all torsion angles of same sign) and triphenylmethyl groups of normal conformation. The analogous (Ph3C)2S6 forms triclinic crystals; the molecular conformation of the C–S6–C chains is not helical, but the motif of torsion angles is + + – – +. In both compounds the C– S bonds are considerably longer (191 pm) than comparable C–S single bonds as in cyclo-C2H4S7. The latter forms monoclinic crystals consisting of ring molecules of C1 symmetry which can formally be derived from the crown-shaped S8 ring by substituting one sulfur atom by a C2H4 group of approximate C2h symmetry.
Insertion von Diphenylcarbodiimid in die Zr–P-Bindung von Cp′2Zr(Cl){P(SiMe3)2} (Cp′ = C5H4Me); Molekülstruktur von / Insertion of Diphenylcarbodiimide into the Zr–P Bond of Cp′2Zr(Cl){P(SiMe3)2} (Cp′ = C5H4Me);
Authors: Hey-Hawkins Evamarie , Lindenberg Frank
Published: March 2015

The reaction of Cp′2ZrCl2 (1) (Cp′ = C5H4Me) with Li(THF)2P(SiMe3)2 yields the zirconoocene monophosphido complex Cp′2Zr(Cl){P(SiMe3)2} (2) in good yield. 2 reacts with diphenylcarbodiimide with insertion of the heterocumulene into the Zr–P bond to give

(3). 2 and 3 were characterized spectroscopically (IR, NMR), and an X-ray structure determination was carried out on 1 and 3 (crystal data: 1, a = 6.803(3), b = 12.008(6), c = 15.480(12) Å, space group Pnma (No. 62), Z = 4, 1685 observed independent reflexions, R = 5.4%, 3, a = 9.210(7), b = 11.491(13), c = 31.279(15) Å, β = 95.32(4)°, space group P21/n (No. 14), Ζ = 4, 6408 observed independent reflexions, R = 6.2%). The crystal structure of 3 revealed η2-bonding (N,N′) of the phosphaguanidene ligand N(Ph)C{P(SiMe3)2}N(Ph)⊖ to the Zr atom (Zr–N 1 2.309(5) Å, Zr–N 2 2.348(5) Å). The ligand can not be obtained from the reaction of Li(THF)2P(SiMe3)2 with diphenylcarbodiimide, which instead affords
Metal Complexes of Dioxo-porphyrins-Zinc(II) Complexes of 2,3,7,8,12,13,17,18-Octaethyl-5,15-dioxo-porphyrin and 5,15-Dioxo-etioporphyrin I
Authors: Senge Mathias O. , Smith Kevin M.
Published: March 2015

The crystal structures of two zinc(II) 5,15-dioxo-porphyrins (porphodimethenes) have been determined to investigate the coordination chemistry of porphyrins with interrupted conjugation system. Both compounds have a five-coordinated zinc center with pyridine as axial ligand and show overall structural parameters very similar to porphyrins. The oxidized meso-positions are, however, easily identified by longer Cm–Ca bond lengths and smaller Ca–Cm–Ca angles. The macrocycles exhibit a small degree of conformational distortion, and the etioporphyrin I derivative shows evidence for π-stacking in the crystal. Crystal data: 1 – C41H47N5O2Zn. Triclinic, a = 10.052(3) Å, b = 14.139(4) Å, c = 14.635(5) Å, α = 105.17(2)°, β = 108.62(3)°, γ = 106.29(2)°, V = 1745.3(9) Å3, CuKα radiation, λ = 1.54178 Å, space group P1̅, Z = 2. R = 0.089. 2 – C37H39N5O2Zn. Triclinic, a = 12.122(3) Å, b = 12.383(3) Å, c = 12.759(4) Å, α = 61.77(2)°, β = 72.19(2)°, γ = 70.32(2)°, V = 1563.8(8) Å3, CuKa radiation, λ = 1.54178 A, space group PĪ, Z = 2, R = 0.076.
Synthesis and Structure of the Hexaethylcyclohexaarsoxane Complexes [ { M(CO)3} 2{cyclo-(C2H5AsO)6}], M = Cr, Mo, W
Authors: Sheldrick William S. , Häusler Thomas
Published: March 2015

The hexaethylcyclohexaarsoxane complexes [{M(CO)3}2{cyclo-(C2H5AsO)6}], M = Cr, Mo, W, 2-4 have been prepared by the reaction of (C2H5AsO)n with the respective metal hexacarbonyl in toluene and characterized by their IR and NMR spectroscopic data. For 2 the molecular structure was established by X-ray structural analysis. The 12 atoms of the As6O6 ring form a flattened cuboctahedron in which the 6 oxygen atoms lie in the central equatorial plane. Cr(CO)3 groups are coordinated facially by the upper and lower three arsenic atoms. An approximately S6 symmetry is displayed by the Cr2As6O6 core. Average values of respectively 116.3 and 98.9° are observed for the As–O–As and O–As–O angles in the hexadentate ligand. The ΕΙ-MS and 1H NMR data for (C2H5AsO)n suggest that this alkylcycloarsoxane is present in solution as a mixture of species including trimers and tetramers so that a metal assisted ring expansion is required for the formation of 2-4.
Kristallstruktur und Schwingungsspektren vom N-Trichlormethyldichlormethyleniminiumhexachloroantimonat CCl2 = NH – CCl3
+SbCl6
- / Crystal Structure and Vibrational Spectra of N-(Trichloromethyl)dichloromethyleniminium Hexachloroantimonate CCl2 = NH—CCl3+SbCl6
-
Authors: Minkwitz Rolf , Lamek Dirk , Preut Hans
Published: March 2015

The crystral structure of CCl2 = NH–CCl3
+SbCl6
- is reported. The compound crystallizes in the monoclinic space group P21/n with a = 11.086(11), b = 9.973(12), c = 14.478(17)Å, β = 106.69(9)°, Ζ = 4. The framework of the cation is planar, with C–N bond lengths of 1.488(7) and 1.280(5)Å. The cation and the anion have one short H ••• Cl contact of 2.313(2)Å.
Synthesis of the Nephritogenoside Trisaccharide Unit Using Phenyl 1-Thioglycopyranoside Sulfoxides as a Glycosyl Donor
Authors: Wang Yali , Zhang Hong , Voelter Wolfgang
Published: March 2015

The nephritogenoside trisaccharide unit was synthesized under mild conditions using phenyl 1-thioglycopyranoside sulfoxides as glycosyl donors. In the coupling process neither thiophenyl nor trityl protecting groups are cleaved from the carbohydrate moieties demonstrating the utility of this method also for oligosaccharide block syntheses.
Synthesis and Crystal Structure of Benzyl (—)-(2S)-1-trityl-2-aziridinecarboxylate
Authors: Korn Andreas , Rudolph-Böhner Sabine , Moroder Luis , Hiller Wolfgang
Published: March 2015

Benzyl (–)-(2S)-1-trityl-2-aziridinecarboxylate (1) has been prepared by the reaction of N-trityl-L-serine benzyl ester and triethylamine in toluene with SO2Cl2. X-ray, 1H NMR and gas chromatographic configuration analysis allowed to define the structure of the compound as a trans-isomer regarding ring substituents and as a (2 S)-enantiomer of the chiral C2.
Notizen: Die Kristallstruktur von MgCl2(1,2-Dimethoxyethan)2 / Crystal Structure of MgCl2(1,2-Dimethoxyethane)2
Authors: Neumüller Bernhard , Stieglitz Gudrun , Dehnicke Kurt
Published: March 2015

MgCl2(DME)2 has been prepared by reaction of MgCl2 with excess dimethoxyethane (DME) in n-pentane solution as white crystals, which are soluble in organic solvents. The crystal structure was determined by X-ray methods. Space group P21/c, Z=4,2512 observed unique reflections, R=0.050. Lattice dimensions at –70°C: a = 1338.9(1), b = 845.1(1), c = 1315.3(2) pm, β = 112.69(1)°. The magnesium atom is in a distorted octahedral coordination by the two chlorine atoms in cis-positions and by the four oxygen atoms of two chelating 1,2-dimethoxyethane molecules.
The Crystal Structure of Lithium fac-Triaquatrisulfitorhodate(III)hydroxide, Li4[Rh(S03)3(OH2)3](OH)
Authors: Mãurer Andreas , Breitinger Dietrich K. , Breiter Roman
Published: March 2015

fac-Li4[Rh(SO3)3(OH2)3](OH) crystallizes in the rhombohedral space group R3-C3
4, Z = 1, in trigonal setting a = 807.7(2), c = 1339.0(3) pm, V = 756.6(2)· 106 pm3, Z = 3. Rh is octahedrally coordinated by three facial S-bonded sulfite groups with Rh—S = 222.6(1) pm and three aqua ligands with Rh—O bonds Rh—O = 217.5(3) pm, elongated by a trans-influence. The average S—O bond length is 148.0(3) pm. All hydrogen atoms have been located. The OH- ion is coordinated exclusively to Li+. The anions are held together by Li+ cations in octahedral environment and by hydrogen bonds of medium strength. Alternatively, the structure can be considered to be built of packages of two oxygen nets and a metal layer, stacked in a sequence similar to that in the CdCl2-structure.