bluuebunny/crossref_metadata_2025 huggingface dataset:
Funktionelle Trimethylphosphinderivate, VI1 Lithium-dimethylphosphinomethanid, (CH3)2PCH2Li, Tetraorganodiphosphinomethane, R2PCH2P(CH3)2 und Tris(dimethylphosphinomethyl)phosphin, P[CH2P(CH3)2]3 Functional Derivatives of Trimethylphosphine, VI1 / Lithium-dimethylphosphinomethanide, (CH3)2PCH2Li, Tetraorganodiphosphinomethanes, R2PCH2P(CH3)2, and Tris(dimethylphosphinomethyl)phosphine, P[CH2P(CH3)2]3
Authors: Karsch Hans H. , Schmidbaur Hubert
Published: March 2015

Dialkylmethylphosphines R2PCH3 are metallated by tert-C4H9Li to give LiCH2PR2 (la: R = CH3, lb: R. = tert-C4H9). la introduces the eCH2P(CH3)2-ligand into L3CoCl to

give [xxx] (2). With diorganochlorophosphines R2PCl (R = CH3, tert-C4H9,

C6H5) and with triphenylphosphite P(O Ø)3 the new biphosphinomethane derivatives (CH3)2PCH2PR2 (4 a-c) and P[CH2P(CH3)2]3 (5) are formed, resp.. Tetramethyldiphosphinomethane (3 a) is also obtained from (CH3)2PCl and Li2CH2. Some properties and spectroscopic data of these new materials are described.
A Study of Vanadium-51 Shielding in VO3+ Compounds
Authors: Rehder Dieter
Published: March 2015

Vanadium-51 NMR chemical shifts δV for a variety of VO3+ compounds have been found to range from —432 ppm (liquid VOBr3) to + 786 ppm (VOF3/CH3CN) relative to a liquid VOCl3 standard. The δV values and hence the shieldings of the vanadium nucleus are shown to increase in the order VOBr3 ≪ VOCl3 < VO(NEt2)3 < VO(OR)3 < VOF3 (1); VOCl3 < VOCl2(OEt) < VOCl(acac)2 < VOCl(OEt)2 < VO(OEt)3 (2); VOCl2(OMe) < VOCl2(OEt) < VOCl2(OPri) < VOCl2(OBut) (3); VO(OEt)3 < VO(OBun)3 < VO(OPrn)3 ≲ VO(OBui)3 < VO(OPri)3 (4). These trends are elucidated by considering the energy separation between highest occupied and lowest unoccupied molecular orbitals (1,2), inductive and π-transmittance of electron density (1, 2), and hindered σ-donation and expansion of the coordination sphere due to ligand bulkiness (3, 4). High solvent shifts in THF solution suggest complete or partial removal of the halogen from the VO3+ moiety for VOBr3 and VOCl2(OBut). For other compounds, solvent shifts of approximately 30 ppm are likely caused by solvation effects. In the case of VOCl3, an equilibrium between solvated VOCl3 and a species containing THF molecules directly bonded to VO3+ is proposed. VOCl3 · 2 RCN (R = Me, Ph) in THF show intact VOCl3 units : solvent-solute interaction is restricted to the second coordination sphere.
Chromchalkogenide, IX1 Ternare Sulfide der Systeme Calcium—Chrom—Schwefel, Strontium—Chrom—Schwefel und Barium—Chrom—Schwefel / Chromium Chalcogenides, IX1 Ternary Sulfides of the Systems Calcium Chromium Sulfur, Strontium Chromium Sulfur, and Barium Chromium Sulfur
Authors: Lutz Heinz Dieter , Becker Rolf-Armin
Published: March 2015

As the first ternary calcium chromium sulfide Ca0,29Cr0,48S was synthesized by firing of stoichiometric mixtures of CaS and Cr2S3 at 950 °C. From strontium and barium only the well-known compounds SrCr2S4 and BaCr2S4 could be obtained. The best methods of preparation for these compounds are the reactions of SrCrO4 or BaCO3 and Cr2S3 resp. with H2S/H2 at 950 °C. Whisker-like single crystals of BaCr2S4 are formed by heating of crude BaCr2S4 with AICl3. X-ray and IR data of the ternary chromium sulfides are given.
Aktive Zentren in CaNaX und NiNaX-Zeolithen / Active Sites in CaNaX and NiNaX Zeolites
Authors: Latzel Johannes , Noller Heinrich
Published: March 2015

Temperature programmed desorption of pyridine and benzene was carried out on NaX-13, CaNaX and NiNaX. This was correlated with IR investigation of pyridine adsorption according to WARD3 and with microcatalytic investigations of 2-butanol dehydration and butene isomerisation. Pyridine showed three definite desorption maxima for each of the three zeolites. While the catalytically inactive NaX-13 desorbed pyridine up to 385 °C, the comparable desorption maxima of the active CaNaX and NiNaX were situated at 490 and 470 °C, respectively. IR investigations showed zeolitic cations for these adsorption centres (bands at 1443-1444,1443-1445,1447-1448 cm-1). The lower desorption temperature of the system pyridine/NiNaX, compared with CaNaX, is incompatible with the higher acidity of Ni2+ and the higher IR band level, while the desorption temperature on NaX-13 and CaNaX is conform with the acidity of the ions and the IR band. Benzene on NiNaX behaves in the same way as on NaX-13 (highest desorption temperature 160 °C) while a desorption peak still occurs at 375 °C on CaNaX. The special case of NiNaX is explained by migration of the Ni2+ into the sodalite cave.
Derivatives of cis-NPCl2 (NSOCl)2 and (NPCl2)2NSOCl, VI Pyridinium Derivatives of cis-NPCl2(NSOF)2 and cis-NPCl2(NSOCl)2
Authors: Iedema A. , Grampel J. C. Van De
Published: March 2015

The compounds with composition NPCl(NSOF)2(C5H5N)OH (1) and NPCl(NSOCl)2 (C5H5N)OH (2) are prepared by reaction of cis-NPCl2(NSOX)2 (X = F, Cl) with pyridine in ether. The pyridinium derivatives are colourless crystalline solids. Tentative structure assignments are given based on NMR data.
Mechanism of the First Order Decay of 2-Hydroxy-propyl-2-peroxyl Radicals and of O2~ Formation in Aqueous Solution
Authors: Bothe Eberhard , Behrens Günther , Schulte-Frohlinde Dietrich
Published: March 2015

Using time resolved ESR spectroscopy and photoflash conductivity the uncatalysed, first order decay of 2-hydroxy-propyl-2-peroxyl radicals and the uncatalysed, first order generation of O2
·̅ and H+ were measured to have the same rate constants. The formation of O2
·̅ and H+ was measured in H2O and D2O and a kinetic isotope effect of kH/k =D3.5 was obtained. Comparing the rate constants of the peroxyl radicals derived from methanol, ethanol and 2-propanol it was shown that the rate constant increases with increasing methyl-substitution. In 2-propanol water mixtures the rate constant of the 2-hydroxy-propyl-2-peroxyl radical increases only slightly with increasing polarity of the solvent. The experimental results are in accord with a mechanism which involves a cyclic transition state leading to a concerted elimination of HO2· followed by dissociation into H+ and O2
·̅.
Juglone and Lawsone as Acid-Base Indicators
Authors: Joshi Krishna C. , Singh P. , Singh G.
Published: March 2015

Juglone and lawsone, both acid-base indicators, obtained from natural sources and give pink and red colours with aqueous alkalies, respectively. Their transition ranges are found to be pH 7.4–8.2 and 2.6–3.4. To establish the transition intervals, a buffer series ranging in the pH values from 2.0–2.2–2.4–2.6–2.8–3.0–3.2–3.4–3.6–3.8–4.0–4.2–4.4–4.6–4.8–5.0–5.2–5.4–5.6–5.8–6.0–6.2–6.4–6.6–6.8–7.0–7.2–7.4–7.6–7.8–8.0–8.2–8.4–8.6–8.8–9.0 has been used. Juglone can be used for the titrations of strong acids with strong bases and weak acids with strong bases and lawsone can be used for the titration of strong acids with weak bases only. Permanancy of the colours at the end point is one of their advantages.
Zur Chemie des Kohlensubsulfids, II Bildung von Thiopyron- und Thiazinthionsystemen / Chemistry of Carbon Subsulphide, II Formation of Thiopyrone and Thiazinethione Systems
Authors: Stadlbauer Wolfgang , Kappe Thomas , Ziegler Erich
Published: March 2015

Carbon subsulphide (C3S2), prepared by pyrolytic reduction of CS2, reacts with 6-chloro-4-hydroxycoumarin and thiobenzamide to yield the polythiopyrones and thiazinethiones 5, 6 and 7. 2-Mercaptopyridine and C3S2 give the mesoionic compound 8. Generally it can be shown that C3S2 reacts to give higher condensed products.
1H- und 13C-NMR-spektroskopische Untersuchung an 1.4-Heteroarsenaniumsalzen / 1H and 13C NMR Spectroscopy of 1,4-Hetero-arsenanium Salts
Authors: Samaan Samir
Published: March 2015

The synthesis of the 1,4-azarsenanium salts 3 and 6 is discribed. Conformation and configuration of the 1,4-oxa- and -azarsenanium salts have been studied via 1H and 13C NMR spectroscopy.
Notizen: Versuche zur Kondensation von Hexamethyl-4.4-bis(methylamino)cyclo-1.2.4-trisila-diazan / Attempts for the Condensation of Hexamethyl-4.4-bis(methylamino)cyclo-1,2,4-trisila-diazane
Authors: Schlingmann Merten , Wannagat Ulrich
Published: March 2015

It was not possible to condensate the Si(NHCH3)2 unit of the title compound to a six-membered ring system. Instead a novel dispiro compound with an OSO unit inside the framework was obtained using (NH4)2SO4 as a catalyst (Scheme 1).
Darstellung und Untersuchung teilweise hydrolysierter Natriumtetrakis(methoxy)borate / Preparation and Investigation of Partially Hydrolyzed Sodium tetrakis(methoxy)borates
Authors: Heller Gert , Horbat Ferdinand
Published: March 2015

By careful hydrolysis of B(OCH3)3 in the presence of NaOCH3 in absolute methanol, crystallized Na[B(OCH3)4] · CH3OH · 1.5 H2O has been prepared. The properties, IR, NMR spectra and X-ray parameters (Pbca; a = 18.2; b = 13.7; c = 19.5 Å; D25
exp = 1.2 g/cm3) are described. The crystal structure was determined by single crystal diffractometer data and refined to a conventional R value of 4.5.
The Photochemically-Induced Degradation of (η5-C5H5)M(CO)3CH3 Complexes (M = Cr, Mo, W)
Authors: Rausch M. D. , Gismondi T. E. , Alt H. G. , Schwäbzle J. A.
Published: March 2015

The photolysis of (η5-C5H5)M(CO)3CH3 complexes (M = Cr, Mo, W) in solvents such as pentane, benzene or tetrahydrofuran results in cleavage of the methyl-metal sigma-bond and formation of the corresponding [(η5-C5H5)M(CO)3]2 analogs as well as methane. Deuterium labeling studies indicate that, for the molybdenum system, abstraction of a hydrogen atom from a cyclopentadienyl ring by the methyl group represents a major reaction pathway for the production of methane. Photolysis of (η5-C5H5)M(CO)3CH3 complexes in CHCl3 produces high yields of [(η5-C5H5)CrCl2]2 in the case of the chromium analog, or (η5-C5H5)M(CO)3Cl where M = Mo or W.
Synthese, Strukturfestlegung und Dissoziationsgleichgewicht eines 15N-markierten Diazadiphosphetidins / Synthesis, Structure Determination, and Dissociation Equilibrium of a 15N-Labeled Diazadiphosphetidine
Authors: Appel Rolf , Halstenberg Mechthild , Knoll Fritz
Published: March 2015

The 15N-labeled diazadiphosphetidine (3a) was prepared to confirm the proposed ring structure by 1H, 31P, 13C, and 15N NMR spectroscopy. The temperature dependence of the NMR spectra suggests a dissociation equilibrium which could be verified by an exchange reaction.
Neue Hochdrucksynthesen von bekannten und unbekannten Derivaten des Co2(CO)8 aus metallischem Kobalt / New High Pressure Syntheses of Known and Unknown Derivatives of Co2(CO)8 Starting from Cobalt Metal
Authors: Behrens Helmut , Hüller Rolf , Jungbauer Anton , Merbach Peter , Moll Matthias
Published: March 2015

The following known and novel cobalt carbonyl complexes are formed by reactions of cobalt metal with bipy, phen, Ph2P-CH2-CH2-PPh2 (P͡P), PPh3, Ph2P-CH2-CH2-NEt2 (P͡N), InCl, SnX2 (X = Cl, Br, I), Cd and HgBr2 under CO pressure (200 bar):

[Co(bipy)3][Co(CO)4]2, [Co(phen)3][Co(CO)4]2, [Co2(P͡P)3(CO)4][Co(CO)4]2; Co2(CO)6 (PPh3)2, Co2(CO)6 (P͡N)2; [Co(CO)4]2SnCl2, {[Co(CO)4]2InCl}2; [Co(CO)3PPh3]2SnX2(X = Cl, Br, I), [Co(CO)3(P͡N)]2SnCl2, [Co(CO)3(P͡N)]2M (M = Cd, Hg).
Über neue Reaktionen substituierter Eisencarbonyle und des Mn2 (CO)10 bzw. Re2(CO)10 mit Natrium-bis [trimethylsilyl]-amid / On New Reactions of Substituted Iron Carbonyls and of Mn2(CO)10 or Re2(CO)10 with Sodium Bis[trimethylsilyl]amide
Authors: Behrens Helmut , Moll Matthias , Popp Werner , Würstl Peter
Published: March 2015

The anionic complexes [(olen)Fe(CO)2CN]- (olen=pentadiene-(1,3), hexadiene-(1,3), 2,3-dimethylbutadiene) and [M2(CO)9CN]- (M = Mn, Re) are formed by the reactions of (olen)Fe(CO)3 or M2(CO)10 (M = Mn, Re) with NaN[Si(CH3)3]2.
Infrarot- und Raman-spektroskopische Untersuchungen an Stereoisomeren eines anorganischen Phosphor-Stickstoff-Ringsystems / Infrared- and Ramanspectroscopic Studies on Stereoisomers of an Inorganic Phosphorus-Nitrogen-Ring-System
Authors: Engelhardt Udo , Jürgens Gerd D.
Published: March 2015

The reaction of MeOP(S)Cl2 with N2H5OH leads to cis- and trans-3,6-dimethoxy-3,6-dithiocyclo-3,6-diphospha-1,2,4,5-tetrazane (1). The configurations of the products are assigned from comparisons of their Raman and IR spectra and from chromatographic and solubility data.
Nitrosylierung von Pentan-2.4-dionato-Kobalt-Komplexen / Nitrosylation of Pentane-2,4-dionato Cobalt Complexes
Authors: Herberhold Max , Kratzer Hans
Published: March 2015

In contrast to tetranuclear bis(pentane-2,4-dionato)-cobalt(II), Co4(acac)8, which is cleaved by nitric oxide to give the adduct Co(acac)2(NO), the mononuclear tris(pentane-2,4-dionato)cobalt(III), Co(acac)3, is attacked by NO at the chelate ligands. The photonitrosylation of Co(acac)8 in benzene or toluene solution leads to the oximato complex tris(3-hydroxyimino-pentane-2,4-dionato)cobalt.
Thienoquinolines, VII. 1 Molecular Orbital Studies of Thieno(2,3-b)quinoline
Authors: Soundararajan Ν. , Shanmugam P.
Published: March 2015

The molecular orbital calculations for thieno(2,3-b)quinoline have been performed within the π-electron framework and by using the CNDO method. The calculated values for internuclear distances, atomic charges and reactivity indices for various types of reactions are presented and discussed.
Notizen: Kristallstruktur von Bariumdigermanid bei hohen Drücken / Crystal Structure of Bariumdigermanide at High Pressures
Authors: Evers Jürgen , Oehlinger Gilbert , Weiss Armin
Published: March 2015

After treatment of orthorhombic (BaSi2 type of structure) bariumdigermanide at 40 kbar and 1000 °C in a belt type apparatus and quenching to ambient conditions a tetragonal polymorph (a-ThSi2 type of structure) is obtained. Its crystal data are: I41/amd, a = 0.4755 nm, c = 1.473 nm, zGe = 0.415.
Notizen: Hochdruckphasen von TlAlSe2 und TIGaSe, mit TlSe-Struktur / High Pressure Phases of TlAlSe2 and TlGaSe2 with TlSe-type Structure
Authors: Range Klaus-Jürgen , Mahlberg Günther , Obenland Sigrid
Published: March 2015

The quenchable high pressure phases of TlAlSe2 and TlGaSe2 are isotypic with TISe.
Darstellung und Kristallstruktur von MgNi2,5B3 und Li1,2Ni2,5B2 / Preparation and Crystal Structure of MgNi2,5B2 and Li1,2Ni2,5B2
Authors: Jung Walter
Published: March 2015

The ternary borides MgNi2,5B2 and Li1,2Ni2,5B2 have been prepared and investigated by X-ray methods. They are isotypic and crystallize hexagonal in the space group P6222—D4
6-with the following constants :

MgNi2.5B2 α = 4.887 ± 0.002 Å, c = 8.789 ± 0.004 Å;

Li1.2Ni2.5B2 a = 4.842 ± 0.002 Å, c = 8.664 ± 0.004 A.

The structure contains boron-pairs and can be derived from the CeCo3B2-type of structure.
The Crystal Structure of the Triiodide of 3,3′ -Bis(dimethylamino)phenothiazine (Methylene Blue)
Authors: Endres H. , Jeromin G. , Keller H. J.
Published: March 2015

The title compound, C16H18N3S · Is, crystallizes in the monoclinic space group P 21/a with a = 11.32(2) Å, b = 16.59(1) A, c = 11.52(2) Å, β = 109.56(8). The structure was solved by Patterson and Fourier methods and refined by least squares to R = 0.066, based on 1042 observed intensities. The planar organic cations form regular stacks along c with interplanar distances of 3.46 Å. The stacks are enclosed by slightly asymetric triiodide anions, which form ribbons perpendicular to the cation stacks.
Über das Verhalten von silicium- und zinnorganischen Verbindungen bei der Synthese von Heterocyclen / On the Behaviour of Silicon and Tin Organic Compounds in the Synthesis of Heterocycles
Authors: Roesky Herbert W. , Zamankhan Hamid
Published: March 2015

The isocyanates of silicon (CH3)2Si(NCO)2 and Si(NCO)4 react with CH3N[Sn(CH3)3]2 and N[Sn(CH3)3]3 to yield the cyclic derivatives 2a-2b as well as the spiro compound 3. The structures of the compounds are discussed on the basis of 1H NMR and IR data. Mass spectra are not conclusive for assigning a certain structure. SO2(NCO)2 and (CH3)3Si-S-Si(CH3)3 form a cyclic compound 4 which contains two sulfur atoms of coordination number two and four. The results of the mass spectra can be interpreted by assuming that a rearrangement occurred. 4 hydrolyses under formation of 5.
1,2,4-Triazole Complexes, III Complexes of Transition Metal(II) Nitrates and Fluoroborates
Authors: Haasnoot Jaap G. , Vos Ger , Groeneveld Willem L.
Published: March 2015

Transition metal(II) fluoroborates and nitrates give various complexes with 1,2,4-triazole. Most of these complexes are expected to be polynuclear. The infrared and ligand field spectra have been used to predict some structural aspects of the compounds. The iron complex shows a low spin → high spin transition on heating.
Metallkomplexe mit Tetrapyrrol-Liganden, XVIII* Osmiumkomplexe des meso-Tetra(p-tolyl)porphyrins / Metal Complexes with Tetrapyrrole Ligands, XVIII* Osmium Complexes of meso-Tetra(p-tolyl)porphyrin
Authors: Buchler Johann W. , Folz Manfred
Published: March 2015

The preparation and spectroscopic characterization of osmium tetra(p-tolyl)porphyrin complexes, Os(TTP)LL′ (2c-21; L or L′ = CO, N2, EtOH, THF, Py, PPh3, P(OMe)3, methoxide or oxide) are described. 2c-21 are compared with the analogous octaethylporphyrin complexes, 1c-11. In 2c-21, the porphyrin ligand is a stronger π-acceptor than in 1c-11. The π-acceptor capacity of the porphyrin ligand renders the dinitrogenosmium(II) porphyrins 1j or 2j less stable than the dinitrogenpentammineosmium(II) cation.
Darstellung von Phthalocyaninen von Ib-Elementen in aprotischen Lösungsmitteln / Preparation of Phthalocyanines of lb-Elements in Aprotic Solvents
Authors: Homborg Heinrich , Kalz Winfried
Published: March 2015

The double decomposition of (TDBA)LiPc(2-) with halocomplexes of the lb-elements is investigated in nonpolar aprotic solvents. Phthalocyanines of the formula MLiPc(2-) are isolated only for the univalent cations Cu(I) and Ag(I), but not for Au(I). The impure AgLiPc(2-) is light sensitive. In contrast to earlier observations only oxidation products of the phthalocyanine anion are obtained in the presence of Cu(II) and Au(III). The preparation of Ag(II) and Au(II) phthalocyanines failed.
N-Sulfonylsulfimides / N-Sulfonylsulfimides
Authors: Roesky Herbert , Aramaki Minoru , Schönfelder Lothar
Published: March 2015

(CF3SO2NSO2)2 (1), a compound with a four-membered ring, was prepared from CF3SO2NSO and SO3. 1 as well as (FSO2NSO2)2 form 1:1 adducts with S4N4 , pyridine and pyridine carbonitrile-4 (2a-2f). By comparison with FSO2NCOS4N4 it was shown that a dipolar type of addition had occured. In contrast the reaction of 1 and (FSO2NSO2)2 with aromatic nitriles yields 1:2 cycloaddition products (3a-3g) which were characterized on the basis of mass spectra. The six-membered rings of 4a-4b which contain carbon, nitrogen and sulfur atoms were obtained from the reaction of isocyanates with (FSO2NSO2)2 or (CF3SO2NSO2)2. 4-BrC6H4NCO and SO3 react in a similar way to yield 5. The starting materials are extremely sensitive to moisture while most of the adducts can be handled in open air without decomposition.
NaMgAs(Sb) -Ternäre Verbindungen mit modifizierter Cu2Sb-Struktur / NaMgAs(Sb) -Ternary Compounds in a Modified Cu2Sb Structure
Authors: Krenkel Burkhard , Schuster Hans-Uwe
Published: March 2015

The compounds NaMgAs and NaMgSb were prepared and their structures determined by powder and single crystal data. NaMgAs and NaMgSb crystallize in a modified Cu2Sb-type-structure, space group P4/nmm-D7
4h. The cell parameters for the tetragonal com-pounds are:
Neue Intercalationskomplexe von Eisen(III)oxichlorid, FeOCl / New Intercalation Complexes of Iron(III) Oxichloride, FeOCl
Authors: Weiss Armin , Sick E.
Published: March 2015

Nonstoichiometric iron (III) oxichloride is capable of intercalating a large number of guest molecules with Lewis base character, e.g. dimethylsulfoxide, formamide, hexa-methylphosphortriamide, or alkylamines, while the reactions of stoichiometric FeOCl are restricted to pyridine and its derivatives only. The nonstoichiometric host lattice can be synthesized either by direct reaction form Fe2O3, FeCl3 and Fe or by reduction of the stoichiometric compound. In the latter case the basal spacings of the intercalation complexes depend upon the degree of reduction and the electrolyte concentration. The highly expanded lattice is rapidly hydrolyzed in the presence of water.
N-Organoquecksilber-triazene - Darstellung und Eigenschaften / N-Organomercury-triazenes - Preparation and Properties
Authors: Peringer Paul
Published: March 2015

The symmetric N-organomercury-triazenes C6H4X-N = N-N(HgC6H5)-C6H4X (X = H, 2-F, 2-Cl, 2-Me, 2-NO2, 3-Cl, 3-NO2, 4-Cl, 4-Me and 4-NO2) were prepared. IR and PMR measurements indicate monodentate structures associated with rapid C6H5Hg exchange in solution. MS and UV data are given.
Reaktionen von Übergangsmetall-Tyrosinkomplexen mit Kaliumnitrosodisulfonat / Reactions of Transition Metal-Tyrosine Complexes with Potassium Nitrosodisulfonate
Authors: Von Martius Konstantin , Schwarzhans Karl
Published: March 2015

Transition Metal-Tyrosine Complexes, Oxidation Tyrosine and the copper(II), cobalt(II) and nickel(II) complexes of this amino acid have been oxidized with potassium nitrosodisulfonate. The chemical oxidation follows the enzymatic pathway, i.e. the Raper-Mason mechanism through the intermediate of dopachrome. The complexes take a considerable shorter reaction time compared with uncomplexed tyrosine. Analytical and spectroscopic data of the resulting black oxidation products indicate a composition comparable with that of natural melanines.
Übergangsmetall-Methylen-Komplexe, VI [1] Zur irreversiblen µ-Methylen/Carbonyl-Isomerie zweikerniger Cobalt-Komplexe mit bifunktionellen Methylen-Liganden / Transition Metal Methylene Complexes, VI [1] On the Irreversible µ-Methylene/Carbonyl Isomerization of Binuclear Cobalt Complexes with Bifunctional Methylene Ligands
Authors: Herrmann Wolfgang , Schweizer Ilona
Published: March 2015

Ethyl diazoacetate (2 a) and tert-butyl diazoacetate (2 b) are converted into the metal stabilized, doubly bridging alkoxycarbonyl carbenes upon photolysis with (ƞ5-C5H5)Co(CO)2 (1) in tetrahydrofurane at -110°C. Although the yields of µ-dicarbonyl-µ-ethoxycarbonylmethylene- bis(ƞ5-cyclopentadienylcobalt) (3 a) and the corresponding ieri-butyl derivative (3b) are low, both compounds attract considerable attention due to an unexpected and hitherto unknown irreversible carbonyl bridge opening process with concomitant µ-methylene rearrangement. These isomerizations have been established by IR and 1H NMR methods to be first order intramolecular processes.
Cleavage Reactions of Oxazolin-5-ones Reactions with 4-Substituted-2-aryl-2-oxazolin-5-ones
Authors: Kassab Nazmi , Harhash Abdul , Elbahaii Said
Published: March 2015

The oxazoline ring in 4-arylazo-2-aryl-2-oxazolin-5-ones (1) is converted to triazolyl-carbonyl amino acids 2, 4 and 6 by the nucleophiles glycine, anthranilic and p-aminobenzoic acids, respectively. The arylidene derivatives 3 of 2-triazolyl-2-oxazolin-5-one were obtained. Triazolylbenzoxazinones 5, were obtained by the ring closure of the amino acid 4.

Grignard's reagent effected ring cleavage of the oxazolinone ring in 4-cinnamylidene-2-aryl-2-oxazolin-5-ones yielding the carbinols 8, the latter cyclizes either in acidic or alkaline medium to afford either benzotropilidenes or oxazolines, respectively.
Notizen: N-Salicyliden-D.L-valinato-thioharnstoffkupfer (II)-Komplex / N-Salicylidene-D,L-valinato-thioureacopper( II) Complex
Authors: Švajlenová O. , Krätsmár-Šmogrović J.
Published: March 2015

N - Salicylidene - D,L - valinato - thiourea - cop - per(U) complex reacts with thiourea to give magnetically diluted stable Cu(II) complex Cu(salal-D,L-val)(tu). This compound shows similar magnetic and spectral properties to those of N-salicyhdene-glycinato-thiourea-copper(II) complex [1].
Notizen: Unusual Formation of Carbamate Salts: an Experimental Proof for the Mechanism of the Removal of Carbobenzoxy Group by Catalytic Hydrogenolysis
Authors: Schőn István , Kisfaludy Lajos
Published: March 2015

Carbamate Salts, Catalytic Hydrogenolysis Catalytic hydrogenolysis of Z-Gly-NH2 and Z-Ala-NH2 resulted in the corresponding free amides and carbamate salts. This observation is a further experimental proof that carbamic acid derivatives are intermediates of hydrogen-olytic removal of carbobenzoxy group under neutral conditions. The ratio of the formation of the two compounds is dependent on the solvent, concentration and chemical structure. The carbamate salts can be acylated without difficulties under the conditions of peptide bond formation.
Die Struktur des Ba3(AsS4)2 · 7H2O / The Structure of Ba3 (AsS4)2 · 7H2O
Authors: Cordier Gerhard , Schwidetzky Christoph , Schäfer Herbert
Published: March 2015

Ba3(AsS4)2 · 7H2O crystallizes in the monoclinic system, space group P21/c (No. 14) with a = 1275.8(4) pm, b = 1282.9(4) pm, c = 1907.7(6) pm, β = 139.5( 1)°. In the structure there are isolated AsS4
3- tetrahedra with As-S-bond lengths between 216.3 and 217.8 pm. The Ba2+ ions are coordinated by a total of 8 to 10 S2- ions and H2O molecules
31P-NMR-und 57Fe-Mößbauer-spektroskopische Untersuchungen an Pentacyano(phosphan oder phosphit)ferraten(II) / 31P NMR and 57Fe Mössbauer Spectroscopic Studies on Pentacyano(phosphane or phosphite)ferrates(II)
Authors: Inoue Hidenari , Sasagawa Masahiro , Fluck Ekkehard
Published: March 2015

The 31P{1H}NMR spectra for a series of pentacyanoferrates(II) of the type Na3[Fe(CN)5L] (L = phosphine or phosphite) have been measured. A low field chemical shift range of 48.1-88.7 ppm for phosphine complexes and of 32.5-48.4 ppm for phosphite complexes is observed when one compares free vs. coordinated ligands. The correlation between chemical shifts in the 31P NMR spectra and isomeric shifts in the Mössbauer spectra is investigated and discussed
Phasenbeziehungen und intermediäre Verbindungen in Systemen GaX3 – Ga2S3 und InX3 – In2S3 (X = Cl, Br, I) / Phase Relations and Intermediate Compounds in Systems GaX3 – Ga2S3 and InX3 – In2S3 (X = Cl, Br, I)
Authors: Kniep Rüdiger , Welzel Wilfried
Published: March 2015

The systems GaX3-Ga2S3 and InX3-In2S3 (X = Cl, Br, I) are quasi-binary and contain the intermediate phases GaSX and InSX with incongruent melting behaviour. Stability regions of GaSCl and GaSBr at elevated temperatures are shifted towards the respective binary halides and include compositions Ga9S8X11 which in an earlier work were reported as separate crystalline phases. InSCl and InSBr (CdCl2-type structure) also show a significant phase width towards the respective binary halides, but with the maximum melting temperature remaining at stoichiometric compositions. Cell parameters and symmetry of InSI are related to InSeI, but do not confirm the proposed isotypic relationship
Ethylene Insertion with Soluble Ziegler Catalysts: Direct Insight into the Reaction Using Enriched 13C2 H4 and 13C NMR Spectroscopy II. The System Cp2TiMeCl/AlMeCl2/13C2H4
Authors: Fink Gerhard , Fenzl Wolfgang , Mynott Richard
Published: March 2015

The elementary processes involved in the polymerization of ethylene by soluble Ziegler catalysts of the type Cp2TiMeCl/AlMeCl2 have been studied by 13C NMR spectroscopy. Using 13C-enriched ethylene, detailed information was obtained directly on the system in the course of the polymerization. No spectroscopic evidence was found for precoordination of the monomer. The development of the oligomer distribution, which could be followed spectroscopically, proves that the mechanism proposed by Olivé cannot be correct. These experiments show conclusively that the ethylene is inserted into the titanium-carbon bond.
Zusammensetzung von Rohsulfan, Nachweis der Sulfane H2S9 bis H2S35 Composition of Crude Sulfane Oil, Identification of the Sulfanes H2S9 to H2S35
Authors: Hahn Josef
Published: March 2015

In benzene solution the position of the 1H NMR signals of sulfanes, H2Sn, strongly depends on the sulfur chain length and on the sulfane concentration. Under proper conditions all sulfanes in a mixture are characterized by well-resolved NMR signals showing a downfield shift with increasing length of the sulfur chain. The shift differences between the higher homologues ( n > 8 ) remain nearly constant, thus allowing the assignment of the signals up to H2S35 and the determination of the complete sulfane distribution in crude oils. In sulfane mixtures without solvent as well as in CS2 and CCl4 solutions, however, H2S8 shows the largest downfield shift. The signals of the higher sulfanes overlap in a narrow range at slightly higher field and cannot be characterized except for the CCl4 solution where an assignment up to H2S11 is possible. The chemical shifts are interpreted in terms of inter- and intramolecular hydrogen bondings. The upfield shift caused by benzene is attributed to the formation of H2Sn · benzene complexes.
Metallkomplexe mit biologisch wichtigen Liganden XXVI : Reaktionen von Bis(α-aminoacidato)platin(II)-Komplexen mit Nitrosylsalzen: Nitrosylplatin-Komplexe[xxx] + X- (X = BF4 , PF6 , SbF6 )/Metal Complexes with Biologically Important Ligands XXXVI : Reaction of Bis(α-aminoacidato) Platinum(II) Complexes with Nitrosyl Salts: Nitrosyl Platinum Complexes[xxx]+X-(X = BF4 , PF6 , SbF 6)
Authors: Ambach Eberhard , Beck Wolfgang
Published: March 2015

The reactions of the glycinato, alaninato, or cyclo-leucinato chelate platinum complexes trans -[xxx] with nitrosyl salts NO+X- (X = BF4, PF6, SbF6) in acetonitrile at -20 °C give the blue nitrosyl compounds {(0N)Pt [xxx] X·nCH3CN. Nitrosation at the amino group is not observed. The spectroscopic data of the nitrosyl complexes (IR, XPE) are reported. [xxx] + PF6
- reacts with lithium halides or halogens in DMF to give the platinum (IV) complexes X2Pt(NH2CH2CO2)2 (X = CI, Br, I).
Neue Verbindungen der Lanthanoiden vom Typ [(C6H5)4E]MX4 · 8 H2O = P, As; M = La, Ce, Pr, Sm, Eu, Gd; X = Cl, Br) / New Lanthanide Compounds of the Type [(C6H5)4E]MX4 · 8 H2O (E = P, As; M = La, Ce, Pr, Sm, Eu, Gd; X = Cl, Br)
Authors: Urland W.
Published: March 2015

The compounds [(C6H5)4P]PrX4 · 8 H2O (X = Cl, Br), [(C6H5)4P]LaBr4 · 8 H2O and [(C6H5)4As]MCl4 · 8 H2O (M = La, Ce, Pr, Sm. Eu, Gd) were prepared and investigated by X-ray diffraction. The compounds were found to be isotypic with [(C6H5)4As]NdCl4 · 8 H2O, which was structurally characterized already previously. The magnetic behaviour of [(C6H5)4P]PrX4 · 8 H2O (X = Cl, Br) has been studied.
Trisubstituted Cyclohexanes / Trisubstituted Cyclohexanes
Authors: Mohrle Hans , Platzek Thomas , Wille Romanus , Wendisch Detlef
Published: March 2015

C-Tertiarv vinylketones or the corresponding masked vinylketone derivatives react with pyrrolidin-2-one in the system sodium hydride.dimethylsulfoxide to substituted cyclohexanes of the 1,3.5- and sometimes additionally of the 1,2.4-type. Only acetophenone Mannich bases bear­ing a p-hydroxy or a dimethylamino group failed in cyclization.
Some Extensions of von Braun (BrCN) Reaction on Organic Bases, Part IV
Authors: Siddiqui Salimuzzaman , Haider S. Imtiaz , Ahmad S. Salman , Siddiqui B. Shaheen
Published: March 2015

Extensions of von Braun cyanogen bromide reaction have been undertaken on some aliphatic and heterocyclic amines. Monocyanamides of all these bases yielded their respective urea and carboxamide derivatives on hydrolysis with dilute hydrochloric acid. They also gave the amido derivatives on reaction with Zn/HCl, as in the case of diisobutyl and di-2-butyl cyanamides.
Notizen: The Isolation and Structure of Papilamine, a New Alkaloid from Buxus papilosa
Authors: Atta-ur-Rahman  , Farhi S. , Miana G. A. , Nisa Mehrun , Voelter Wolfgang
Published: March 2015

A new alkaloid, papilamine, has been isolated from the leaves of Buxus papilosa to which the structure 1 has been assigned on the basis of chemi­cal and spectroscopic studies.
Oxidative Knüpfung einer Phosphor-Phosphor-Bindung unter Einwirkung von Ag(I)- bzw. Cu(II)-Ionen: Synthese und Struktur von [(C6H5)PH2Ag{μ-(C6H5PH)2}]2 (AsF6)2, einem sechsgliedrigen Silber-Phosphor-Ring / The Oxidative Formation of a Phosphorus-Phosphorus Bond in the Presence of Ag(I) and Cu(II) Ions: Synthesis and Structure of [(C6H5)PH2Ag{μ-(C6H5PH)2}]2 (AsF6)2, Containing a Six-Membered Silver-Phosphorus Ring
Authors: Jones Peter G. , Roesky Herbert W. , Grützmacher Hansjörg , Sheldrick George M.
Published: March 2015

The reaction between AgAsF6 and phenylphosphine proceeds with formation of a phosphorus-phosphorus bond. The main product 1, [(C6H5)PH2Ag{μ-(C6H5PH)2}]2 (AsF6)2, was characterized by an X-ray structure determination [P1̄, a = 919.0(4), b = 1109.8(4), c = 1316.4(5) pm, α = 97.48(3), β = 107.25(3), γ = 102.71(3)°, Z = 1, R = 0.057 for 2806 observed reflections], 1 contains Ag2P4 rings; the silver atoms are further coordinated by phenylphosphine ligands, thus acquiring trigonal coordination geometry. A similar reaction is observed with Cu(AsF6)2, forming the analogous Cu(I) complex 2.
Rearrangement of 14β-Hydroxy-12β-sulfoxy-steroids to 13,17-Seco-12,17-cyclo-steroids; a 2D-NMR Analysis
Authors: Habermehl Gerhard G. , Hammann Peter E.
Published: March 2015

The rearrangement of 3-oxo-14β-hydroxy-12β-methanesulfoxy-card-20(22)-enolide and 14β-hydroxy-12β-methanesulfoxy-pregnane-3,20-dione during elimination of the sulfoxygroups was studied. By means of 2D-NMR analysis the structures were determined as 13,17-seco-12,17-cyclo-steroids.
2,5-Dihydro-1,2,5-azoniastannaboratole: Nützliche Vorstufen für die Heterocyclensynthese / 2,5-Dihydro-1,2,5-azoniastannaboratole: Useful Steps for the Synthesis of Heterocycles
Authors: Kerschl Susanna , Wrackmeyer Bernd
Published: March 2015

Organoboration, Heterocycles, Multinuclear NMR 1,1-Organoboration of diethylamino-dimethyl-(1-propynyl)stannane (6), formed by an exchange reaction between the bis(propynyl)-(4) and bis-(diethylamino)dimethylstannane (5), with trimethyl-(2a) or triethylborane (2b) leads to highly reactive new heterocyclic compounds (7). Both, the coordinative N→B and the weak Sn-N bond are readily attacked by H-acidic compounds. Ammonia or primary amines are used as examples. Multinuclear NMR (1H, 11B, 13C, 15 N, 119Sn) data serve for the characterization.
Schwefeldiimid, S(NH)2, und monosubstituierte Schwefeldiimide, S(NR)(NH), mit R = tert-Butyl und Trimethylsilyl / Sulfur Diimide, S(NH)2, and Monosubstituted Sulfur Diimides, S(NR)(NH), with R = tert-Butyl and Trimethylsilyl
Authors: Herberhold Max , Jellen Wolfgang , Bühlmeyer Wolfgang , Ehrenreich Wolfgang , Reiner Josef
Published: March 2015

The unstable parent compound of the sulfur diimides, S(NH)2 (1), has been obtained in solution by stoichiometric protonation of the anion SN2
2- in K2SN2 with acetic acid. An analogous protonation of the salts S(NR)(NK) leads to the m onosubstituted sulfur diimides S(NR)(NH) containing bulky substituents such as R = tert-butyl (2) and R = trimethylsilyl (3); 2 and 3 can be isolated as white solids below -40 °C. The temperature-dependent 1H NMR spectra of 1-3 indicate the presence of two isomers in solution (ratio 4:1) which are reversible interconverted.
Metallkomplexe mit biologisch wichtigen Liganden, XL [1]. Iridium(III)-Komplexe mit 9-Methylguanin / Metal Complexes with Biologically Important Ligands, XL [1]. Iridium(III) Complexes with 9-Methylguanine
Authors: Bauer Herbert , Sheldrick George M. , Nagel Ulrich , Beck Wolfgang
Published: March 2015

The dinitrogen-tetrafluoroborato complex (Ph3P)2(Cl)(N2)(H)IrFBF3 reacts with 9-m ethylguanine in CH2Cl2 to give [(Ph3P)2(Cl)(H)Ir(9-methylguanine)]+BF4
- (2). From a solution of 2 in methanol the complex (Ph3P)2(Cl)2(H)Ir(9-methylguanine) (3) is obtained. The reaction of [(Ph3P)2(Cl)(N2)(H)IrOSO2C4F9] with 9-methylguanine affords the com plexes [(Ph3P)2(Cl)(N2)(H)Ir(9-methylguanine)]+C4F9SO3
- (5) and [(Ph3P)2(Cl)(H2O)(H)Ir(9-methylguanine)]+ C4F9SO3
- (6). The coordination of the guanine derivative to the iridium atom in 2, 5, 6 is discussed on the basis of the infrared spectra. The crystal structure of 3 was determined. 9-Methylguanine is coordinated via N (7). Intermolecular hydrogen bonding between the chloro-ligand and HN (1) of guanine leads to linear chains in the crystal.
Beiträge zur Chemie des Phosphors, 156 [1, 2]. 1.2-Di-tert-butyl-cyclotriphosphan, (t-BuP)2PH, und 1.2.3-Tri-tert-butyl-cyclotetraphosphan, (t-BuP)3PH / Contributions to the Chemistry of Phosphorus, 156 [1.2] 1,2-Di-tert-butyl-cyclotriphosphane, (t-BuP)2PH, and 1,2.3-Tri-tert-butyl-cyclotetraphosphane, (t-BuP)3PH
Authors: Bäudler Marianne , Makowka Bernd , Langerbeins Klaus
Published: March 2015

The partially substituted cyclotriphosphane (t-BuP)2PH (1) has been obtained by hydrolysis of KP(t-BuP)2 and by the reaction of (t-BuP)2PSiMe3 with methanol, respectively. In contrast to the fully tert-butyl substituted cyclotriphosphane (t-BuP)3, 1 is not stable at room temperature, but decomposes favoring the rearrangement into the cyclotetraphosphane (t-BuP)3PH (2). The 31P NMR parameters of 1 and 2 are reported and discussed.
Beiträge zur Chemie des Siliciums und Germaniums, XXXIX [1]. Darstellung, Eigenschaften und 29Si-NMR-Spektren von höheren Kaliumsilanylen KSinH2n+1 / Contributions to the Chemistry of Silicon and Germanium, XXXIX [1]. Preparation, Properties and 29Si-NMR Spectra of Higher Potassium Silanyls
Authors: Fehér Franz , Krancher Michael
Published: March 2015

Diluted solutions of potassium disilanyl, 2-potassium trisilanyl and 2-potassium isotetrasilanyl in m onoglym e have been prepared from potassium silyl and di- or trisilane under suitable reaction conditions. The purity of the silanyls varies between 95 and 99%. Their stability increases from potassium di- to 2-potassium isotetrasilanyl. The 29Si NMR spectra exhibit a strong high field shift for the metal substituted silicon atoms and a m oderate low field shift for the other silicon atoms compared with the signals of the corresponding silanes.
Dicyanphosphid-Reaktionen [1] / Dicyanophosphide Reactions [1]
Authors: Schmidpeter Alfred , Bürget Günther
Published: March 2015

31P (and, as applicably, 77Se) NMR spectra show P(CN)2
- to take up one or two atoms of sulfur or selenium and to react with a variety of anionic phosphorus nucleophiles. Displacement of the first cyanide gives cyanodiphosphides, cyanophosphinidene-phosphates, -phosphinates, -thiophosphinates and -iminophosphinates, respectively. Displacement of the second cyanide gives triphosphates and triphosphinates which are otherwise known as products from the nucleophilic P4 degradation.
(AsPh4)4[CrCl4(μ-N2S2)]4 · 8 CH2Cl2; Synthese, IR-Spektrum und Kristallstruktur / (AsPh4)4[CrCl4(μ-N2S2)]4 · 8 CH2Cl2; Synthesis, IR Spectrum and Crystal Structure
Authors: Wadle Heribert , Dehnicke Kurt , Fenske Dieter
Published: March 2015

Trithiazylchloride, (NSCl)3, reacts with metallic chromium, with chromium hexacarbonyl, with CrCl3·3 thf, as well as with chromium(VI) oxide to form mixtures, in which S4N3
⊕ [CrCl4(N2S2)]⊖ can be identified as the major product. This compound reacts with tetraphenylarsonium chloride in dichloromethane to form the title compound, which we have characterized by IR spectroscopy and an X-ray crystal structural analysis. (AsPh4)4[CrCl4(N2S2)]4·8 CH2Cl2 crystallizes monoclinically in the space group C2/c with four formula units per unit cell and with the following lattice constants at -100 °C: a = 2146, b = 2033, c = 3137 pm; β = 96.0° (9918 independent observed reflexions, R = 0.064). The compound consists of AsPh4
⊕ ions, tetrameric anions [CrCl4(N2S2)]4
4⊖ and included CH2Cl2 molecules. The chromium atoms of the anions occupy the corners of a nearly ideal square; they are connected via the N-atoms of planar N2S2-rings, which are oriented perpendicularly to the Cr4-plane. The chromium atoms complete their distorted octahedral coordination with four terminal chlorine atoms, the axial ones of which form short Cl···S-contacts of average 310 pm to the S-atoms of the N2S2-rings.
Pyridin-Borabenzol und Pyridin-2-Boranaphthalin als Liganden von Metallen der Chromgruppe / Pyridine-borabenzene and Pyridine-2-boranaphthaline as Ligands of Group 6 A Metals
Authors: Boese Roland , Finke Norbert , Keil Thomas , Paetzold Peter , Schmid Günter
Published: March 2015

Pyridine-borabenzene (1) and pyridine-2-boranaphthalene (2) can be coordinated to group 6A metals M to form compounds of the type (OC)3M·1 and (OC)3M·2, respectively. X-ray structure determinations prove the ligands to be η6-bonded to the metal via the boron-containing six-membered ring.
Cyclothiazeno-Vanadiumdibromid, VBr2(N3S2) / Cyclo-Thiazeno Vanadium Dibromide, VBr2(N3S2)
Authors: Hanich Jürgen , Willing Wolfgang , Müller Ulrich , Dehnicke Kurt
Published: March 2015

VBr2(N3S2) was synthesized by reaction of VCl2(N3S2) with Me3SiBr. It reacts with PPh4Br in dibromomethane solution to form (PPh4)2[VBr3(N3S2)]2. The compounds were characterized by their IR and 51V NMR spectra. The crystal structure of VBr2(N3S2) was determined by X-ray diffraction (2060 reflexions. R = 0.114). Crystal data: triclinic, space group P1̄, a = 586.4, b = 794.2, c = 744.6 pm. α - 89.25, β - 108.58, γ = 99.67°. Z = 2. The vanadium atoms form planar, six-membered rings wjith the N3S2 groups, with short VN distances (172 and 185 pm). Bromine- bridged dimers are associated via V−N links to form chains in a similar way as in some tetrahalides. The structure is similar to that of VCl2(N3S2), but the chains are rotated by 17° along their axes.
Metallorganische Verbindungen der Lanthanoide, XXXIII [1] Dicyclopentadienyllanthanoid-alkyle und -hydride von Neodym, Samarium und Lutetium [2] / Organometallic Compounds of the Lanthanides, XXXIII [1] Dicyclopentadienyllanthanide Alkyls and Hydrides of Neodymium, Samarium and Lutetium [2]
Authors: Schumann Herbert , Jeske Gerald
Published: March 2015

Tricyclopentadienylneodymium and -lutetium react with sec-butyl lithium and terf-butyl lithium to form sec-butyl- and tert-butyl(dicyclopentadienyl)neodymium and -lutetium, which decompose to the corresponding dicyclopentadienyllanthanide hydride complexes. Dicyclopentadienyl-bis-(trimethylsilyl)methylsamarium and -lutetium are made from dicyclopentadienylsamarium or -lutetium chloride and bis(trimethylsilyl)methyl lithium. They react with hydrogen to form the corresponding dicyclopentadienyllanthanide hydride complexes.
Reaction of Quinones with Nitrosoarenes
Authors: Forrester A. R. , Thomson R. H.
Published: March 2015

The structure of the dinitrone formed on reaction of nitrosobenzene with 1,4-benzoquinone has been confirmed by spectroscopic measurements. An electron transfer radical-anion mechanism is suggested to account for its formation.
Reaction of Malononitrile and Ethyl Cyanoacetate: a Novel Synthesis of Polyfunctional Pyridine Derivatives
Authors: Mohareb R. M. , Fahmy S. M.
Published: March 2015

Malononitrile reacts with ethyl cyanoacetate to give a polyfunctional substituted pyridine derivative 5. The latter compound reacts with aniline, hydrazines and aromatic aldehydes to give condensated products. The active methylene of 5 couples with benzenediazonium chloride to give the phenylhydrazone derivative which cyclises readily to give a pyrido[2,3-d]pyridazine deriva­tive. 5 reacts with trichloroacetonitrile, and carbon disulphide to give fused heterocyclic deriva­tives.
[(Methoxythio)carbonyl]pyridin-Derivate, eine neue Verbindungsklasse aus Pseudomonas putida [1] / [(M ethoxythio)carbonyl]pyridine Derivatives, a New Class of Compounds from Pseudomonas putida [1]
Authors: Hildebrand U. , Taraz K. , Budzikiewicz H.
Published: March 2015

From the culture medium of Pseudomonas putida three pyridine derivatives were isolated which contain the (methoxythio)carbonyl (CO−S-OCH3) group thus far not described in the literature. Characterization and structure elucidation are reported.
Ba2Sb3, eine neue Zintlphase mit Sb6-Ketten / On Ba2Sb3, a New Zintl Phase with Sb6-Chains
Authors: Eisenmann Brigitte , Jordan Hanna , Schäfer Herbert
Published: March 2015

The new compound Ba2Sb3 crystallizes in the monoclinic system, space group P21/c (No. 14) with the lattice constants a = 693.4(3) pm, b = 1345.3(6) pm, c = 1581.7(6) pm, β = 90.25(15)°.

The compound is isotypic to the Sr2Sb3 structure with discrete Sb6
8- chain anions
Preparation, Structure and Physical Properties of BEDT-TTF* Nitrates
Authors: Weber A. , Endres H. , Keller H. J. , Gogu E. , Heinen I. , Schweitzer D.
Published: March 2015

Electrocrystallization of BEDT -TTF in THF with tetrabutylammonium nitrate as supporting electrolyte leads to the deposition of at least three different phases. The a-phase (C10H8S8)3(NO3)2, Mt = 1277.98, crystallizes in the monoclinic space group P21/n. The structure of this solid was solved: a = 5.890(2), b = 31.125(10), c = 12.915(6) Ä , β = 103.73(3)°, V = 2300 Å 3, Z - 2, Dx = 1.84 gem-3, MoKfα λ = 0.7107 Å , μ = 11.2 cm-1, F(000) = 1300, room temperature, R = 0.057 for 1888 observed independent reflections. Sheets of BEDT-TTF radical cations with short intermolecular S···S contacts (>3.315(4) Å ) are separated by anion layers. Two more BEDT-TTF nitrates have been characterized by their unit cell data. Results of temperature dependent electrical conductivity and thermopower measurements on crystals of the a-phase are presented. They are metallic down to about 30 K
Chloronitrosylkomplexe von Ruthenium(II) Die Kristallstruktur von (PPh3Me)2[Ru(NO)Cl4]2-2 CH2Cl2 / Chloro Nitrosyl Complexes of Ruthenium (II) The Crystal Structure of (PPh3Me)2 [Ru(NO)Cl4]2 • 2 CH2Cl2
Authors: Fenske Dieter , Demant Udo , Dehnicke Kurt
Published: March 2015

Ruthenium trichloride, obtained from its hydrate with thionyl chloride, reacts with excess trichloronitrom ethane yielding polymer [Ru(NO)Cl3]; by addition of triphenylmethylphosphonium chloride in dichlorom ethane (PPh3Me)2[Ru(NO)Cl4]2 · 2 CH2Cl2 is obtained, the IR spectrum of which is reported and assigned. Its crystal structure was determined with X-ray diffraction data (6404 independent observed reflexions, R = 0.068). Crystal data at -90 °C: a = 1145, b = 1591, c = 1406 pm, β = 96,0°, Z = 2, space group P21/C. The structure consists of PPh3Me⊕ cations, centrosymmetric anions [Ru(NO)Cl4]2
2⊖ nearly fulfilling C2h symmetry, and CH2Cl2 molecules. In the anions the Ru atoms are linked via chloro bridges; the nitrosyl groups occupy axial positions with bond distances RuN of 175 and NO of 113 pm, bond angle RuNO 172.7°.
Zur Stereochemie des freien Elektronenpaares in Verbindungen des vierwertigen Tellurs: Verzerrtes TeCI6
2-Oktaeder in [H3N(CH2)3NH3TeCI6 regulär oktaedrisches Anion in H3N(CH2)3NH3SnCI6 / On the Stereochemistry of Lone Pair Electrons in Compounds with Tetravalent Tellurium: Distorted TeCl6
2-Octahedron in [H3N(CH2)3NH3]TeCl6, Regular Octahedral Anion in [H3N(CH2)3NH3]SnCl6
Authors: Abriel Walter , Friedrich Claudia
Published: March 2015

Using 293 K diffractometer intensity data, the structures of [H3N(CH2)3NH3]TeCl6 and [H3N(CH2)3NH3]SnCl6 have been determined by single crystal X-ray technique and refined to a final of 0.027 and 0,029, respectively. The yellow crystals of the tellurate are orthorhombic (space group Pnma) with a = 22.952(2), b = 7.5414(4), c - 7.801(1) Å and Z = 4. This structure contains distorted TeCl6
2- octahedra (distances Te - Cl min. 2.426(1), max. 2.672(1) Å ) with approximate 2mm point symmetry. In contrast, the SnCl6
2- ion in the second title com pound is octahedral with only small deviations from m 3m symmetry (distances Sn -Cl mean: 2.438(3) Ä ). The colourless crystals of this tin com pound are orthorhombic (space group Pnma) with a - 17.6082(9), b = 7.1809(3), c = 10.190(1) Å and Z = 4. Considering the TeX6
2- (X = Cl, Br, I) salts known to date, a distorted species is an exception, although a distortion is predicted by the VSEPR theory. The results agree with the rules for the appearance of a static stereochemical effect of the lone pair electrons in the TeX6
2- species
NaLiS: Ein weiteres Interalkalimetallsulfid / NaLiS: A nother Inter Alkaline Metal Sulphide
Authors: Sabrowsky Horst , Thimm Alfred , Vogt-Mertens Petra
Published: March 2015

The colourless com pound NaLiS has been prepared and its structure determined by single crystal X-ray diffraction techniques. The very hygroscopic NaLiS crystallizes in the tetragonal space group P4/nmm (Z = 2) with the cell parameters a = 402.6(1), c = 649.5(2) pm. The structure was solved from 720 counter reflections (216 symmetry independent reflections) by differential Fourier syntheses. Refining gives a least squares residue of 0.024.

The anti-PbFCl-type structure is characterized by layers of LiS4/4-tetrahedra connected by their edges in two dimensions and 2 interspersed layers of sodium