bluuebunny/crossref_metadata_2025 huggingface dataset:
Ferric Chloride Induced Dehydrodimerization of Tetrahydrocarbazole
Authors: Mester I. , Ernst L. , Das B. P. , Choudhury B. , Chowdhury D. N.
Published: February 2015

Ferric chloride induced dehydrodimerization of 1,2,3,4 -tetrahydro -9 H-carbazole (1) gives product 6 , the structure of which was established on the basis of its spectroscopic properties. The 1H and 13C chemical shifts of the aromatic part of 1, as well as of 4a-methyl-2,3,4,4a-tetrahydro-1 H-carbazole (7a) and 4a-phenyl-2,3,4,4a-tetrahydro-1H-carbazole (7b) have also been securely assigned.
Organocobalamin Reactions Relevant to the Mechanism of the α-Methyleneglutarate Mutase Enzyme [1]
Authors: Grate Jay W. , Schrauzer Gerhard N.
Published: February 2015

The organocobalamin with methylitaconic acid attached to cobalt via its methyl group has been synthesized for the first time. This compound is believed to be an intermediate in the interconversion of methylitaconic acid and α-methyleneglutaric acid, catalysed by the coenzyme B12-dependent α-methyleneglutarate mutase enzyme. Reactions of this organocobalamin and the corresponding dimethyl ester demonstrate that cleavage of the Co-C bond leads to the rearranged α-methyleneglutarate structure under conditions where intermediate carbanions are formed.
Activated Nitriles in Heterocyclic Synthesis: The Reaction of Substituted Cinnamonitriles with 2-Functionally Substituted Methyl-2-thiazolin-4-one Derivatives
Authors: Sadek Kamal Usef , Hafez Ebtisam Abdel Aziz , Mourad Abo-Elfetouh E. , Elnagdi Mohamed Hilmy
Published: February 2015

A variety of thiazolo[2,3-a]pyridine and 3-(2-thiazolin-2-yl)pyridine derivatives were synthesised via the reaction of arylsubstituted cinnamonitrile derivatives with 2-functionally substituted 2-thiazolin-4-one derivatives. Thiazolo[2,3-a]pyridines were also obtained on reacting arylsubstituted cinnamonitriles with thioglycolic acid in ethanolic triethylamine solutions.
Elektronenspinresonanz-Untersuchungen an Amavadin, einem vanadiumhaltigen Naturstoff / Electron Spin Resonance Investigations of Amavadine, a Natural Product Containing Vanadium
Authors: Krauß P. , Bayer E. , Kneifei H.
Published: February 2015

ESR spectra indicated that amavadine contains tightly bound oxovanadium (IV ). Identical ESR spectra were obtained from biological material as well as from isolated and synthesized amavadine. The ESR hyperfine structure of oxidized amavadine can be interpreted assuming the formation of a nitroxyl radical.
BaTe3, das erste binäre Erdalkalipolytellurid / BaTe3, the First Binary Alkaline Earth Polytelluride
Authors: Cordier Gerhard , Schwidetzky Christoph , Schäfer Herbert
Published: February 2015

BaTe3 crystallizes in the tetragonal system (space group: P421m) with the lattice constants:

a = 791.5(3) pm , c = 443.0(5) pm, c/a = 0.560.

The new compound is isotypic to BaS3 and BaSe3 and contains bent Te3 anions.
The Isolation and Structure of Karachicine — a New Alkaloid from Buxus papilosa
Authors: Atta-ur-Rahman  , Nisa Mehrun
Published: February 2015

A new alkaloid, karachicine, has been isolated from the leaves of Buxus papilosa to which structure 1 has been assigned.
Classical One Step Syntheses of Monoand Di-Nitrate Sugars via Triflates
Authors: Afza Nighat , Malik Abdul , Voelter Wolfgang
Published: February 2015

A new approach for the synthesis of some sugar nitrates is described. The reaction sequence consists of esterifying partially protected carbohydrates with trifluoromethanesulfonic anhydride and reacting the resulting triflates with tetrabutylammonium nitrate. This procedure is mild, convenient and has the advantage of protecting highly acid-labile groups.
Reaktionen und Strukturen von [(C2H5)4N][OsCl6] und [(n-C4H9)4N]2[Os2Cl10] / Reactions and Structures of [(C2H5)4N][OsCl6] and [(n-C4H9)4N]2[Os2Cl10]
Authors: Krebs B. , Henkel G. , Dartmann M. , Preetz W. , Bruns M.
Published: February 2015

On heating of [(C2H5)4N][OsCl6] for a short time at 240 °C , Cl2 is lost and [(C2H5)4N]2[Os2Cl10] is formed quantitatively. Both complexes are connected by a temperature dependent redox equilibrium so that by treatment at 120 °C with Cl2 gas the hexachloroosmate(V) is recovered from the decachlorodiosmate(IV). The crystal structures of salts of both an ions were determined from single crystal X -ray diffraction analyses. [(C2H5)4N][OsCl6] is monoclinic, space group P2 1 with a = 7 .020 (1), b = 10 .163 (2), c = 11.609 (2) Å , β = 103.91(1)° (at - 133 °C ). The strongly pseudocentrosymmetric structure shows a reversible phase transition at ca. 85 °C. The Os -Cl bond length (mean value 2.303 Å) in the regular [OsCl6]-octahedra is significantly smaller than in [OsCl6]2− , in accordance with vibrational spectra. [(n -C4H9)4N]2 [Os2Cl10] crystallizes in the orthorhombic space group Pbca with a = 15 .496 (2), b = 15 .965 (3), c = 19 .431(3) Å and contains centrosymmetric [Os2Cl10]2− ions with approximate D2h symmetry. Within the edge-sharing [OsCl6] octahedra the mean terminal and bridging Os -Cl bond lengths are 2.307 and 2.411 Å , respectively.
Reversible Redox-Reaktionen von Cyanothiomolybdaten — Elektrochemische Untersuchungen an [Mo3S4(CN)9]5− und [Mo4S4(CN)12]8− / Reversible Redox Reactions of Cyanothiomolybdates — Electrochemical Properties of [Mo3S4(CN)9]5− and [Mo4S4(CN)12]8−
Authors: Wieghardt K. , Herrmann W. , Müller A. , Eltzner W. , Zimmermann M.
Published: February 2015

The tri- and tetranuclear clusters [Mo3S4(CN)9]5− and [Mo4S4(CN)12]8− , the structures of which are known, show the following reversible redox reactions in solution:
Die Kettenstruktur der hydratisierten Tetramethylammoniummangan(II)-hexacyanometallate(III) NMe4MnFe(CN)6 · 8 H2O und NMe4Mn2(CN)6 · 8 H2O / The Chain Structure of the Hydrated Tetramethylammoniummanganese(II)-hexacyanom etallates(III) NMe4MnFe(CN)6 · 8 H2O und NMe4Mn2(CN)6 · 8 H2O
Authors: Henkel H. , Babel D.
Published: February 2015

The crystal structures of the isomorphic tetragonalcompounds NMe4MnFe(CN)6 ·8 H2O (a = 1067.0, c = 1056.8 pm ) and NMe4Mn2(CN)6 · 8 H2O (a = 1066.9, c = 1064.1 pm ), space group P4/n, Z = 2 , were determined (R = 0 .03). The structure is built up from slightly distorted M(CN)6
3− octahedra and square planar Mn(H2O)4
2+ cations, stacked one upon the other in nearly eclipsed positions to form cyanobridged chains - Mn -NC -Mm -CN -along [001]. The average distances in the compounds are: Fe -C = 193.8 (Mn -C -199.3) pm, C -N = 114.7 (114.7 ) pm , Mn -N = 220 .2 (218 .2) pm, Mn -O = 218 .8 (218 .5) pm. The differences of bridge lengths are discussed, as well as the orientation and contact distances of the tetramethylammonium cations. These and additional crystal water, forming H -bonded(H2O)4 rings, occupy positions in the center of elpasolite- like sub cells, which result from O -H ··· N bridging between different chains. Some further relations to the structures of elpasolite and prussian blue are pointed out.
Darstellung und Charakterisierung von Silathia- und Silasela-Grundkörpern / Synthesis and Characterisation of Silathia and Silasela Basic Compounds
Authors: Haas Alois , Hitze Reiner , Krüger Carl , Angermund Klaus
Published: February 2015

For the synthesis of the compounds ClH2SiESiH3, (H3SiE)2SiH2 and (HSi)4E6, (H3Si)2E was used as a chalkogenating agent(E = S,Se). With H2SiCl2 and HSiCl3, respectively, pure samples were isolated only of (H3SiS)2SiH2, (HSi)4S6 and (HSi4Se6. The others were characterised by spectroscopic investigations. An X-ray structure determination for (HSi)4S6 was carried out and a few chemical properties of these substances are described.
X-Ray Structure of a Nickel(II) Complex of the Tetra-N-methylated Macrocycle Dibenzocyclam with a Folded Ligand Configuration
Authors: Elias Horst , Grewe Rüdiger , Klaehn Dirk-Detlev , Paulus Helmut
Published: February 2015

Under mild conditions nickel(II) nitrate reacts with the macrocyclic N4 ligand TMBC ( = 1,4 ,8,11-tetramethyl-1,4,8,11-tetraazadibenzo[b,i]cyclotetradecane) to form the light blue-green complex Ni (TMBC) (NO3)2. A three-dimensional X-ray diffraction study shows that the complex crystallizes in the monoclinic space group P21/c with a = 896.1(3) pm, b = 2059.9(7) pm , c = 1298.6(6) pm, β = 91.37(1)° and Z = 4. The nickel is six-coordinate. The distorted octahedral N4O2 arrangement of donor atoms around the nickel is formed by the tetradentate N4 macrocycle TMBC in an unexpected folded form and by a nitrate ion as a bidentate ligand occupying two depositions. The structure could be refined to the final R-value of 0.045 only by assuming disorder for the second, noncoordinated nitrate ion.
Synthese und Struktur vierfach ortho-substituierter Bis(phenyl)platin(II)-Verbindungen / Synthesis and Structure of Tetra-ortho-substituted Bis(phenyl)platinum(II) Compounds
Authors: Brune Hans Albert , Wiege Manfred , Debaerdemaeker Tony
Published: February 2015

Experiments to synthesize tetra-ortho-substituted cis-bis(phenyl)platinum (II) compounds yielded exclusively the trans-isomers trans -bis(2 ,6 -bis methoxyphenyl)bis(triphenylphosphane)- platinum(II) (trans-1a) and trans -bis(2 ,4 ,6 -trismethoxyphenyl)bis(triphenylphosphane)- platinum(II) (trans-1b), instead of the cis-compounds. The structure of trans-1b has been determined by X-ray analysis.
NMR-spektroskopische Untersuchungen an 1,1-Thiophendioxid und verwandten Verbindungen / NMR Spectroscopical Investigations of Thiophene 1,1-Dioxide and Related Compounds
Authors: Meier Herbert , Molz Thomas , Kolshorn Heinz
Published: February 2015

The 1H and 13C NMR data of thiophene 1,1-dioxide (3) and related compounds, especially of the precursor 2 and the consecutive product 5 are evaluated by computer simulation and multiple resonance. Chemical shifts and coupling constants reveal that 3 has the character of a cyclic diene. Diatropic or paratropic effects can be excluded.
Reactivity of the Bis(phenyldithiocarbazato)cobalt(II) Complex Towards Nitrogen, Phosphorus, and Oxygen Donors
Authors: Aiy Aref A. M. , Alla Mohamed A. Abd , Mohamed Ahmed A. , Mousa Mahmoud A.
Published: February 2015

The preparation of the following mixed ligand complexes has been described; Co(pdtc)2(phos)m [pdtc = phenyldithiocarbazate and phos - triphenylphosphane (tpp), bis- (diphenylphosphino)methane (dpm), bis(diphenylphosphino)ethane (dpe), bis(diphenylphosphino) propane (dpp), or bis(diphenylphosphino)butane (dpb); m = 1 or 2], Co(pdtc)2(amine)n [amine = o-phenanthroline (o-phen), Triethylamine (tea), quinoline (quin), α-picoline (α -pic), or β-picoline (β-pic); m = 2 or 4], and Co(pdtc)2(oxygen donors)x [oxygen donors = n-BuOH or phenylacetamide (paa); x = 1 or 2]. The compounds have been characterised by chemical analysis, molar conductance measurements, electronic and IR spectra. Pseudooctahedral geometries are proposed for all the complexes. The phenyldithiocarbazate anion acts as a bidentate ligand in the SN coordination mode. The biological screening of the prepared complexes has been carried out on some pathogenic bacteria and fungi.
Derivate des 1.3-Benzdioxols, 51 Darstellung und Reaktionen des 6.7.8.9-Tetrahydrocyclohepta[4.5]benzo[1.2-d][1.3]dioxol-5-on / Derivatives of 1,3-Benzodioxoles, 51 Preparation and Reactions of 6,7,8,9-Tetrahydrocyclohepta[4.5]benzo[1,2-d][1,3]dioxol-5-one
Authors: Dallacker Franz , Tumbrink Ludwig
Published: February 2015

A synthesis of substituted phenylvaleric acids 4 a-e from 1,3-benzdioxolaldehyds 1a -d is described. Treatment with PPA gave benzocycloheptanones 5a-e which gave by reduction and dehydratisation benzocycloheptene 7 a-d. Reactions of benzocycloheptanone 5a and of benzocycloheptenaldehyds 10a-b are reported.
Elektrochemische Synthesen, XI Katalyse-Anwendung elektrochemischer Systeme: Hydroformylierungsreaktionen / Electrochemical Syntheses, XI Catalysis Application of Electrochemical Systems: Hydroformylation Reactions
Authors: Grobe Joseph , Zimmermann Heinz
Published: February 2015

The electrochemical synthesis of Co2(CO)6(PBu3)2 and [Co(CO)3(PBu3)2][Co(CO)4] from Co(acac)2 or cobalt anodes has been investigated. The formation of the catalytically active species HCo(CO)4 and HCo(CO)3PBu3, respectively, by electrochemical reductive carbonylation under conditions suitable for oxo-reactions was ascertained by IR-spectroscopic studies. Further investigations demonstrate the possibility of simultaneous production of the catalysts and application in hydroformylation processes with the advantage of reducing the induction period and the amount of catalyst for equal quantities of products.
Vergleichende Röntgenstrukturanalysen von Naphthothiadiazinen und isovalenzelektronischen Naphthotriazinen Röntgenstrukturanalysen von Acenaphthyleno[5,6-cd][1,2,6]- thiadiazin, 2-Methyl-2 H-acenaphthyleno[5,6-de]-1,2,3-triazin und Naphtho[1,8-de]thiadiazin / Comparison of Naphthothiadiazines and Isoelectronic Naphthotriazines by X-Ray Structural Analysis X-Ray Structural Analyses of Acenaphthyleno[5,6-cd][1,2,6]thiadiazine, 2-Methyl-2 H-acenaphthyleno[5,6-de]-1,2,3-triazine and Naphtho[1,8-de]thiadiazine
Authors: Gieren Alfred , Lamm Viktor , Haddon Robert C. , Kaplan Martin L. , Perkins M. John , Flowerday Peter
Published: February 2015

We have performed an X-ray structural analysis of the sulphur diimide 1 and the isoelectronic triazine 2. In addition we found two crystal modifications of the sulphur diimide 3, which is an analogue of the previously characterized 4, but the modification suitable for X-ray analysis (tetragonal, β) was disordered. From the bond lengths of 1 and 2 results, that in both cases there is only a weak π-interaction between the SN2 or the N3R group and the acenaphthylene system. For chalcogen diimides and triazines with a peri connection of the X N2 (X = S, Se) or N3R groups, respectively, at the naphthalene system , the bond lengths of the connecting C - N bonds are correlated with the bond lengths within the naphthalene system. The compounds 1 and 2 occupy differing positions at the least squares line resulting from values of five compounds. The higher ordinate and the smaller abszissa for the position of 1 suggests slightly higher bond order for the S - N bonds in 1 in comparison with the N -N bonds in 2, and bonding relationships, which are not identical in 1 and 2, as can also be deduced from the bond lengths in question.
Heterocyclische Siebenring-Verbindungen, XXVII Darstellung und thermisches Verhalten von substituierten 1,2-Dimethyl- 4-phenyl-l-benzothiepinium-Salzen Heterocyclic / Seven-membered Ring Compounds, XXVII Synthesis and Thermal Reactivity of 1,2-Dimethyl-4-phenyl-1-benzothiepinium Salts
Authors: Hofmann Hans , Löw Gerhard
Published: February 2015

The 1,2-dimethyl-4-phenyl-1-benzothiepinium salts 2a-c have been prepared by alkylation of the parent 1 -benzothiepins 1a -c with methyl fluorosulfonat and their thermal behaviour was investigated with regard to the formation of sulphur-free reaction products.
Notizen: A Palladium — Assisted Generation of Fulvene
Authors: Crisp G. T. , Holle S. , Jolly P. W. , Mynott R. , Werner H.
Published: February 2015

Palladium -fulvene complexes of the type [Pd(η2- R2C:C5H4)L2] may be prepared by reacting monosubstituted-η5 -cyclopentadienyl-palladium-η3-allyl complexes with tertiary phosphines
Metallacycloalkane, VIII η5-Cjclopentadienyl-η2-methylencyclopropan-Cobaltkomplexe und deren Umwandlung in η4-Butadien-Cobaltkomplexe über Cobaltacyclopentane/ Metallacycloalkanes. VIII η5 -Cyelopentadienyl-η2-Methylenecyclopropane Complexes of Cobalt and their Transformation into η4-Butadiene Complexes via Cobaltacyclopentanes
Authors: Binger Paul , Martin Tony Ronald , Benn Reinhard , Rufińska Anna , Schroth Gerhard
Published: February 2015

The η5-cyclopentadienyl-bis(η2-methylenecyclopropane)cobalt complexes 5 and 6 were prepared by reaction of CpCo-bis(ethylene) (4) with methylenecyclopropane (1) and 2,2,3,3-tetramethylm ethylenecyclopropane (2), which on heating isomerise via non-isolable cobaltacyclopentanes and 4-m ethylene-cobaltacyclohexanes to give the CpCo-1,3-butadiene derivatives 10, 11 and 12. The same type of isomerisation can be observed by reacting CpCo(triphenylphosphane)( acrylonitrile) with 1 leading to the CpCo-1,3-butadiene derivative (15). With diphenylm ethylenecyclopropane (3) only a CpCo-monomethylenecyclopropane complex is formed, which isomerises immediately to give CpCo(1,1-diphenyl-1,3-butadiene) (13) and in minor amounts the fluxional binuclear cobalt complex 14. All new cobalt complexes were fully characterised by means o f high resolution NM R spectroscopy.
Katalytische Synthese von Hydridmagnesiumchlorid aus Magnesium, Wasserstoff und Magnesiumchlorid/ Catalytic Synthesis of Hydridomagnesium Chloride from Magnesium, Hydrogen and Magnesium Chloride
Authors: Bogdanović Borislav , Schwickardi Manfred
Published: February 2015

THF solutions of hydridomagnesium chloride (HMgCl, 1a) can be prepared in nearly quantitative yields by hydrogenation of magnesium in THF solutions of magnesium chloride at 0 °C in the presence of a CrCl3-Mg anthracene catalyst. Concentration of saturated HMgCl solutions, or hydrogenation of magnesium under the above mentioned conditions in MgCl2-THF suspensions, lead to the formation of THF solutions of species having the approximate com position HMgCl · MgH2 or 2 HMgCl · MgH2.
Organoboron-Monosaccharides, XIII β-D-Mannofuranosides: Highly Stereoselective Syntheses and NMR Characterization
Authors: Dahlhoff Wilhelm Volker , Geisheimer Angelika , Schroth Gerhard , Mynott Richard
Published: February 2015

Stoichiometric reactions of 2,3:5,6-di-O-ethylboranediyl-α-D -mannofuranosyl bromide (1) with O -nucleophiles at room temperature give β-D-mannofuranosides with excellent stereoselectivities. The labile glycosides obtained are deboronated in quantitative yields and then converted to their tetra-O -acetates. The products are characterized by NMR spectroscopy.
Über die katalytische Umwandlung von Olefinen, VIII „Nacktes“ Nickel als Katalysator bei der Umalkylierung von Aluminiumtrialkylen mit α-Olefinen/ The Catalytic Conversion of Olefins, VIII „Naked“-Nickel as a Catalyst for the Transalkylation of Aluminium Trialkyls with α-Olefins
Authors: Fischer Karl , Jonas Klaus , Mollbach Alfred , Wilke Günther
Published: February 2015

Nickel(0)-olefin complexes such as tris(ethylene)nickel(0) (4), tris(bicycloheptene)nickel(0) (6 ), all-transcyclododecatriene)nickel(0) (26), tris(stilbene)nickel(0) (27) and bis(cyclooctadiene) nickel(0) (23) are highly active homogeneous catalysts for the transalkylation of aluminium trialkyls with α-olefins. After com pletion of the reaction the nickel(O) can be rem oved in the form of Ni(CO)4 by reaction with CO. Characteristic for the catalytic reaction is the formation of olefin-nickel-π-bonds and Ni -C -Al multi-centre-bonds. The mechanism o f the reaction is discussed with the help of m odels.
Diboran(4)-Moleküle mit Boratomen unterschiedlicher Koordinationszahl/ Diborane(4) Molecules with Boron Atoms with Different Coordination Number
Authors: Haubold Wolfgang , Hrebicek Johann , Sawitzki Gisela
Published: February 2015

Molecules with directly bonded boron atoms with different coordination numbers (10, 11, 12 and 13) can be prepared from suitable bifunctional bases like 6, 7, 8 or 9 and C12B - BC12 (1) in an appropriate solvent at high dilution. Properties and spectroscopic data - including 1J(11B-11B) - are described. The molecular structure of 10 was investigated by means of an X-ray structure analysis.
Nickel(0)-katalysierte Synthese von Iminen aus Isocyanaten und Aldehyden/ Nickel(0) Catalysed Synthesis of Imines from Isocyanates and Aldehydes
Authors: Hoberg Heinz , Sümmermann Klaus
Published: February 2015

The influence of different ligands upon the nickel(0)-catalysed formation of imines from isocyanates and aldehydes is reported. Carbonyl-free nickel(0) systems are found to be more active and provide a simple synthesis of imines. The catalysis proceeds via a five-membered metallacycle, which has been isolated and characterized.
Organoborierung von Alkinylstannanen, XIV Organoborierung von Bis(alkinyl)stannanen: Mechanismus und Anwendung der 119Sn–NMR-Spektroskopie/ Organoboration of Alkynylstannanes, XIV Organoboration of Bis(alkynyl)stannanes: Mechanism and Application of 119Sn NMR Spectroscopy
Authors: Kerschl Susanna , Wrackmeyer Bernd
Published: February 2015

Dimethylbis(phenylethynyl)stannane (1) reacts with trialkylboranes, BR3 (2), to give bis(alkenyl stannanes (5) (R = C2H5), 1-bora-4-stanna-2,5-cyclohexadienes (6 ) (R = C2H5, C3H7
i), 1- stanna-2,4-cyclopentadienes (7) (R = C2H5) and l-stanna-3-cyclopentenes (8 ) (R = CH3, C2H5). 13C and 119Sn NMR data prove the structure of the reaction products (5 to 8 ). 119Sn NMR is useful (i) for following the course of the reaction (mechanism!) and (ii) for quantitative analysis of the product distribution. Deorganoboration reactions play an important role in the formation of the various heterocyclic systems.
1,1-EMborierung von 1-Trimethylsilylalkinen/ 1.1-Diboration of 1-Trimethylsilylalkines
Authors: Klusik Hartmut , Pues Christine , Berndt Armin
Published: February 2015

1,2-Di-terr-butyl-l,2-dichlorodiborane(4) (1) and l,2-dichloro-1,2-bis(dimethylamino)- diborane(4) (2) add to 1-trimethylsilylalkines 3 a -3d to yield 1,1-bis(rm-butylchloroboryl)- alkenes (4) and 1, 1-bis(chlorodimethylaminoboryl)alkenes (5), respectively, while reaction of 1 with acetylene, trimethylsilylacetylene, 2-butine and 3-hexine leads to 1,2-bis(tert-butylchloroboryl) alkenes (7). Compounds 4, 5 and 7 are characterized by MS. 1H, 13C and 11B NMR spectroscopy.
Bis[(η3-allyl)nickel(μ,η5-2,3-dihydro-1,3-diborolyl)]nickeI-Tetradecker- Komplexe mit terminalen Allylliganden/ Bis[(η3-allyl)nickel(μ,η5-2,3-dihydro-1,3-diborolyl)]nickel Tetradecker Complexes with Terminal Allyl Ligands
Authors: Kuhlmann Thomas , Siebert Walter
Published: February 2015

Reactions between bis(allyl)nickel complexes and alkyl derivatives of 2,3-dihydro-1,3-diborole (1a, b) in refluxing toluene or mesitylene yield deeply colored solutions. By distillation and chromatography the first η3-allyl tetradecker complexes 8 were obtained in 4 -15% yield. In the violet residues higher molecular species are present, which could not be identified. The red, oily tetradeckers are characterized by NMR and mass spectra; their formation is discussed.
Topological Effect on MO Energies, IX. On Topologically Related 1,4-Dibora-2,3-diazarine and 1,4-Dibora-2,5-diazarine
Authors: Motoc loan , Polansky Oskar E.
Published: February 2015

Minimal STO-NG (N = 3, 4 and 6 ) basis set non-empirical HF SCF MO calculations have been performed for topologically related 1,4-dibora-2,3-diazarine (S) and 1,4-dibora-2,5-diazarine (T). The equilibrium geometries of these S and T isomers have been computed by symmetry-constraint geometry optimizations using the STO-3G basis set. The calculations lead to the prediction that: i) the T isomer is about 48 kJ/mole less stable than the S isomer, and ii) the π -MO energy patterns of the S and T isomers are in complete agreement with the TEMO theorem, while the bonding σ-MO eigenvalues exhibit four inversion points.
Beiträge zur Chemie des Bors, 148. Diamidobor(1+)-Kationen aus Bis(amino)borhalogeniden durch Halogenid-Abspaltung/ Contributions to the Chemistry of Boron, 148.Diamidobor(1+) Cations from Bis(amino)borhalogenides by Halide Abstraction
Authors: Nöth Heinrich , Rasthofer Bernhard , Weber Siegfried
Published: February 2015

Bis(amido)boron(1 + ) cations can be generated from bis(amino)-boron halides and an appropriate halide acceptor. The ease of formation of the diethylamido-2.2.6.6-tetramethylpiperidinoboron-( 1 + ) cation 5 from diethylamino-tetramethylpiperidino-boron halides has been studied and found to increase with decreasing strenght of the boron halogen bond. In the case of bis(2.2.6.6- tetramethyl-piperidino)boron fluoride AlCl3, BCl3, BBr3 and even BF3 give access to salts of the bis(tetramethylpiperidino)boron-(1+ ) cation. The tetrabromoborate salt 7c reacts with Ag-triflate to yield the corresponding tetratriflatoborate 7g. Similarly. bis(tetramethylpiperidino)boron chloride 8 , obtained from the tetrachloroborate 7b in boiling pyridine, readily gives bis(tetramethylpiperidino) boron(1 + )-tetrachlorometalates. Bis(tetramethylpiperidino)boron(1 + )-triflate is formed by reaction of 8 with AgOSO2CF3.
1,3,5-Tri-tert-butyl-2,4,6-triisopropyl-3,5-diaza-1-azonia-2,6-dibora- 4-borata[2.2.0]bicyclohexan, der erste Vertreter der Dewarborazine/ 1,3,5-Tri-tert-butyl-2,4,6-triisopropyl-3,5-diaza-1-azonia-2,6-dibora- 4-borata[2.2.0]bicyclohexane, the First Dewar Borazine
Authors: Paetzold Peter , Plotho Christoph von , Schmid Günter , Boese Roland
Published: February 2015

The iminoborane iPr-B ≡ N -tBu (1a), metastable at -78 °C, trimerizes to form (iPrBNtBu)3 (4a) at elevated temperatures. The determination of the molecular and crystal structure reveals 4a to be a Dewar-borazine-type molecule with two short peripheral BN-double-bonds (136 and 138 pm) and an extra-long bridge BN-single-bond (175 pm). The same trimer 4a is formed by addition of la to the diazadiboretidine-type dimer (iPrBNtBu)2, prepared independently. The ethyloboration and the azidoboration of la with BEt3 and Me3SiN3, respectively, and the cycloaddition of PhN3 to 1a follow expected patterns.
Azaborolinyl-Komplexe, XV. Bis(η5-1,2-azaborolinyI)ruthenium-Sandwichkomplexe – Darstellung und Strukturuntersuchung/ Azaborolinyl Complexes, XV. Bis(η5-1,2-azaborolinyl)ruthenium Sandwich Complexes – Synthesis and Structure Investigation
Authors: Schmid Günter , Boltsch Ottmar , Bläser Dieter , Boese Roland
Published: February 2015

The synthesis of bis(1-tert-butyl-2 -methyl-η5 - 1 ,2 -azaborolinyl)ruthenium (1) and bis(2-methyll- trimethylsilyl-η5 - 1 ,2 -azaborolinyl)ruthenium (2) succeeds when RuCL is reacted with the corresponding 1,2-azaborolinyl lithium compounds in THF at -70 °C. Each of the sandwich complex forms two isomers with a clockwise and an anti-clockwise conformation of the azaborolinyl rings. The anti-clockwise isomer of 1 (1a ) gives colourless crystals which were investigated by singlecrystal X-ray diffraction methods. The molecular structure shows the rings in an eclipsed orientation forming an interplanar angle of 8.6 °. The isomers of 1 as well as of 2 give different 1H and 11B NMR signals.
N-Methylcarbamoylphosphate, II. Thermische Zersetzung/ N-Methylcarbamoyl Phosphates, II. Thermal Decomposition
Authors: Seel Fritz , Klein Norbert
Published: February 2015

The thermal decomposition of various salts of mono-N-methylcarbamoyl and bis-N-methylcarbamoyl phosphoric acid in aprotic and protic solvents (acetonitrile, trichlorom ethane, alcohols) and in the solid state has been studied in detail. Final products are mono-, di-, poly-, and cyclophosphates, in addition phosphoric acid esters if alcohols are used as solvents; and either sym. dimethylurea or methyl isocyanate and methylamine.

The spontaneous decomposition of sparingly soluble N-methyl carbamoyl phosphates in aqueous suspensions to yield slightly soluble diphosphates demonstrates clearly that the reaction of calcium hydrogen phosphate with alkali cyanates via calcium carbam oylphosphate to give calcium diphosphate - which has been considered a prebiotic key reaction - is not a result of a special feature of the structure of the intermediate product.
Die Kristallstruktur von Di-μ-oxo-cis-dioxo-dichloro-bis(2,2′ -bipyridyl)- molybdän(V) (Mo–Mo)-Nitromethansolvat, Mo2O4Cl2(bipy)2 · CH3NO2/ Crystal Structure of Di-μ-oxo-cis-dioxo-dichloro-bis(2,2′-bipyridyl)- molybdenum(V) (Mo–Mo) Nitromethane Solvate, Mo2O4Cl2(bipy)2 ´ CH3NO2
Authors: Beck Johannes , Hiller Wolfgang , Schweda Eberhard , Strähle Joachim
Published: February 2015

Mo2O4Cl2(bipy)2 has been obtained by oxidation of MoCl4(bipy) with O2 in ethanol/H2O . The complex crystallizes from CH3NO2 with one solvent molecule per formula unit in the monoclinic space group P 21/n: a = 954.1(2), b = 1925.3(2), c = 1423.2(2) pm, β = 102.48(2)°, Z = 4. The characteristic unit Mo2O4
2+ of the dinuclear complex consists of two terminal oxo ligands in a cisarrangem ent and two bridging oxygen atoms forming a non-planar Mo2O2 ring. A strong Mo -Mo single bond is indicated by a short distance of 256.5 pm. The coordination of both Mo atoms is completed by a Cl atom and a chelating bipyridyl ligand.
Übergangsmetall-substituierte Phosphane, Arsane und Stibane, XLY. Einige Komplexe mit Dreiringstruktur: Aufbau aus Metallo-arsinsulfiden. Öffnung des Metallacyclus mit Phosphordonoren / Transition-Metal Substituted Phosphanes, Arsanes and Stibanes, XLV. Some Complexes with a Three Membered Ring Structure: Formation from Metallo-arsinesulfides. Opening of the Metallacycle with Phosphorus Donors
Authors: Luksza Michael , Malisch Wolfgang
Published: February 2015

The interaction of the metallo-arsanes Cp(OC)2(L)W - AsR2(1a -c) with elemental sulfur or selenium leads to the formation of the metallo-arsinesulfides (selenides) Cp(OC)2(L)W -AsR2(S,Se) (2a-c), which are converted to the metallacyclic complexes

(3a, b) with loss of CO on refluxing in pentane. While the

of 3b is cleaved at the W -S bond by (MeO)3P to give Cp(OC)2[(MeO)3P]W -AsMe2(S), (4), with an A s-bonded η1-thioarsinyl ligand, Me3P preferentially cleaves the W -As bond in 3b, d to produce Cp(OC)2(Me3P)W -S -AsR2 (5a, b), in which the R2As-S-unit is S-coordinated. The spectroscopic data of the new complexes are reported and discussed with respect to the dynamic behaviour of the compounds.
Metallkomplexe mit biologisch wichtigen Liganden, XXXIII. Reaktionen von α-Aminosäuren und α-Aminosäurederivaten mit Gold(III)-chlorid/ Metal Complexes with Biological Important Ligands, XXXIII. Reactions of α-Amino Acids and Derivatives there of with Gold(III) Chloride
Authors: Ambach Eberhard , Singh Mano Mohan , Nagel Ulrich , Beck Wolfgang
Published: February 2015

The hydrochlorides of a-aminoacid esters react with Au2Cl6 in thionyl chloride to give the ammonium salts [H3NCHRCO2R′]+AuCl4
- (R = H , Me, R′ = H , Me, Et). The X-ray structure of [H3NCH(Me)CO2Me]+AuCl4
- has been determined. The reactions of a-aminoacids with Au2Cl6 in SOCl2 afford mixtures of ammonium tetrachloroaurate(III) salts with a-amino acids, a-amino acid chlorides or a-amino acid anhydrides as amine components. Cysteine esters reduce gold(III) to give the gold(I) compounds [AuSCH2CH(N H2)CO2R]n (R = Me, Et).
Notizen: Ba3Sn2As4, eine neue Zintlphase mit Kettenstruktur/ On Ba3Sn2As4, a New Zintl Phase with Chain Structure
Authors: Eisenmann Brigitte , Jordan Hanna , Schäfer Herbert
Published: February 2015

The new compound Ba3Sn2As4 crystallizes in the monoclinic system (space group: P21/c, No. 14) with the lattice constants

a = 806.6(5) pm , b = 1986.1(8) pm ,

c = 793.1(5) pm , β = 112.3(1)°. The compound is isotypic to Sr3Ge2As4.

Octahedral Sn2As6 units are connected by common edges to chains.
Notizen: Reaction Product of Formaldehyd and O-Benzylhydroxylamine: A Schiff Base?
Authors: Respondek Johannes
Published: February 2015

200 MHz 1H and 50 MHz 13C NMR spectra were recorded from the reaction product of form aldehyd 1 and O -benyzlhydroxylamine 2 for the purpose of its structure elucidation
Notizen: A Dipole Moment Study of Prostaglandins F1α and F1β
Authors: Pappalardo Giuseppe C. , Grassi Antonio , Nicolini Marino , Lumbroso Henri
Published: February 2015

The experimental electric dipole moments in dioxane solution, together with the calculated dipole moments for some selected conformers, are reported for the two natural prostaglandins F1α and F1β. The results obtained are compatible with a hypothesized hairpin structure for these molecules in solution.
Kristallstruktur- und MoBbauer-Untersuchungen am Lithiumhexacyanoferrat(III)-Hexamethylentetramin-Addukt Li3[Fe(CN)6] ·2C6H12N4 · 5H20 / Crystal Structure and Mossbauer Studies of the Lithium Hexacyanoferrate(III)-Hexamethylenetetramine Adduct Li3[Fe(CN)6] · 2C6H12N4 · 5H2O
Authors: Pickardt Joachim , Kahler Jorg , Rautenberg Norbert , Riedel Erwin
Published: February 2015

Crystals of the adduct Li3[Fe(CN)6] · 2C6H12N4-5H2O are orthorhombic, space group I2mm, Z = 2, a = 909.4(5), b = 1046.1(5), c = 1455.8(5) pm. The structure may be regarded as a packing of Fe(CN)6 octahedra and hexamethylenetetramine molecules. The lithium ions are coordinated to nitrogen atoms of both groups and to water molecules. Mossbauer spectra have been recorded for the temperature range between 290 K and 77 K. At all temperatures the spectra show two doublets with nearly identical isomer shifts but different quadrupole splittings, thus indicating the presence of two kinds of hexacyanoferrate(III) ions with slightly different distortions of the ligand spheres around the Fe atoms. The effect is discussed on the assumption of a statistical distribution of one of the lithium ions.
Chloroantimonate(III), V. Darstellung und Kristallstruktur des Triethanolammoniuin-tetrachloroantimonats [(C2H4OH)3NH]SbCl4 / Chloroantimonates(III), V. Preparation and Crystal Structure of Triethanolammonium Tetrachloroantimonate [(C2H4OH)3NH]SbCl4
Authors: Brodalla Dieter , Lipka Annegret
Published: February 2015

Triethanolammonium tetrachloroantimonate was synthesized and investigated by X-ray diffrac­tion analysis. The structure consists of SbCl3 molecules, chloride ions and triethanolammonium cations. The SbCl3 molecules and the cations form adducts by a bridging O-atom at 274.3 pm. The Sb-Cl distances within the SbCl3 molecule are 239.2, 240.3 and 245.3 pm, whereas the distances from the Sb atom th the Cl- ion are 290.2 and 332.1 pm.
Zweikernige Komplexe des Molybdan(III): Die Kristallstruktur von μ-Bromo-μ-hydroxo-bis- [bromo(1,4,7-triazacyclononan)molybdan(III)]dibromid · Tetrahvdrat Dinuclear / Complexes of Molybdenum(III): The Crystal Structure of μ-Bromo-μ-hydroxo-bis- [bromo(1 ,4,7-triazacyclononane)molybdenum(III)]dibromide · tetrahydrate
Authors: Chaudhuri P. , Wieghardt K.
Published: February 2015

The syntheses of two binuclear complexes of molybdenum(III) is reported. The oxidation of LMo(CO)3 (L = 1,4,7-triazacyclononane, C6Hi5N3) with bromine in chloroform (0.75% ethanol) yields the monomeric complex [MovLOBr2](Br3) (μeff(298 K) = 1.61 μB). Reduction of this species in aqueous solution with Zn under an argon atmosphere at 25 °C affords - upon addition of NaBr - green crystals of [Mo2L2(μ-OH)(μ-Br)Br2]Br2 · 4H2O. The reduction at elevated temperatures yields green crystals of [Mo2L2(μ-OH)2Br2]Br2 ·2 H2O. Both complexes exhibit antiferromagnetic behaviour. The crystal structure of [Mo2L2(μ-OH)(μ-Br)Br2]Br2 · 4 H2O con­sists of dinuclcar cations, bromide ions and water of crystallization. It crystallizes in the triclinic space group P1 with cell constants a = 821.3(3). b = 837.7(2), c = 1008.1(3) pm, α = 103.63(2)°, β = 98.92(2)°, γ = 79.54(2)° and Z = 1. The two Mo(III)-centers are in a distorted octahedral environment of the tridentate amine, a terminal bromo-ligand and one hydroxo- and one bromide bridging ligand (edge sharing). The short Mo-Mo distance of 255.8(3) pm indicates strong metal- metal bonding.
Reaktionen des (2-TrimethylsiIoxyphenyl)diphenylphosphans mit Phosphorhalogeniden – Kristall- und Molekiilstruktur des (2-Hydroxyphenyl)diphenylphosphoniumbromids / Reactions of (2-Trimethylsiloxyphenyl)diphenylphosphane with Phosphorus Halides – Crystal and Molecular Structure of (2-Hydroxyphenyl)diphenylphosphonium Bromide
Authors: Schmutzler Reinhard , Schomburg Dietmar , Bartsch Rainer , Stelzer Othmar
Published: February 2015

Reaction of hexamethyldisilazane with (2-hydroxyphenyl)diphenylphosphane 1 affords the trimethylsilyl derivative 2-(Me3SiO)-C6H4-PPh2 (2). The Si-O-bond is cleaved by various phos­phorus halides, e.g. [Bun
3PF]+ Br-, PhPCl2, PCl3, Ph2PF3 and PhPF4 with formation of the cor­responding P-O-derivatives and trimethylfluoro- or trimethylchlorosilane, respectively. The 31P{1H} NMR spectra of the products are discussed. [2-(Bun
3PO)-C6H4-PPh2]+Br- (7) on reac­tion with nickel(II) bromide forms a paramagnetic complex of composition NiBr2L2 (L = 7). A distorted tetrahedral coordination geometry at Ni may be derived from its magnetic moment, electronic spectra and conductivity data. The structure of the hydrobromide of 1 shows strong hydrogen bonding between the OH- and PH-group of the cation and the bromide anion (P-H 1,42 Å, H···Br 2,41 Å, angle P-H···Br 150°; O-H 1,00 Å, H···Br 2,09 Å, angle O-H···Br 176°).
Darstellung und Schwingungsspektren von Fluoro-Chloro-Iridaten(IV) einschließlich der Stereoisomeren / Preparation and Vibrational Spectra of Fluoro-Chloro-Iridates(IV) Including Stereoisomers
Authors: Tensfeldt D. , Preetz W.
Published: February 2015

The reaction of [IrCl6]2- with BrF3 generates the mixed complexes [IrFnCl6-n]2-, n = 1-5, of which the species with n = 2, 3, 4 are ds-configurated. Due to the stronger trans-effect of Cl as compared to F on treatment of [IrF5Cl]2- and cis-[IrF4Cl2]2- with SOCl2 the trans-isomers are formed stereospecifically. The pure fluoro-chloro-iridates(IV) are separated by ion exchange chromatography on diethylaminoethyl-cellulose. The vibrational spectra of the mixed ligand complexes are completely assigned according to point groups D4h, C4v, C3v, and C2v. The IrCl stretching vibration of [IrF5Cl]2- is split by the isotopes 35C1 and 37Cl, showing two well resolved sharp Raman lines at 361 and 355 cm-1.
Cvclopentadienvlrhenium-Komplexe mit Schwefelbrücken: Die Strukturen von Cp2Re2(CO)4S und Cp2Re2(CO)2S5 / Cyclopentadienylrhenium Complexes Containing Sulfur Bridges: The Structures of Cp2Re2(CO)4S and Cp2Re2(CO)2S5
Authors: Herberhold Max , Reiner Dietmar , Ackermann Klaus , Thewalt Ulf , Debaerdemaeker Tony
Published: February 2015

The coordinatively unsaturated fragment [CpRe(CO)2], prepared by photolytic CO elimination from cyclopentadienyl tricarbonylrhenium, CpRe(CO)3 (1), reacts with either S8 or COS to give rhenium-sulfur complexes such as CpRe(CO)2S2 (2), Cp2Re2(CO)4(μ-S) (3), and Cp2Re2(CO)2(μ-S2)(μ-S3) (4). The X-ray crystal structures of the binuclear complexes 3 and 4 were determined: 3 contains a three-membered ring with a S atom bridging a formal Re-Re single bond (Re1 - Re2 2.946(1) Å. Re 1-S-Re2 76.4(1)°), while in 4 two sulfur-chain frag­ments, S2 and S3, are used to bridge the two Re atoms in a seven-membered 1,4-dirhenia cycloheptasulfur ring.
Die Bildung von Fluorisocyanat (F–NCO) in Argonmatrix / Formation of F–NCO in an Argon Matrix
Authors: Gholivand Khodayar , Willner Helge , Bielefeldt Dietmar , Haas Alois
Published: February 2015

Matrix samples of F-CO-N3, and X-CO-NF2 (X = H, NF2, CF3) were photolyzed by mercury arc light and the new infrared bands at 2172, 861, 695, 646, 529 cm-1 assigned to the F-NCO molecule. 15N isotopic substitution confirmed the assignment of the IR bands of the new compound.
Isotopic Effect on X-Nuclei Screening and X–H(D) Scalar Spin-Spin Coupling in XH4 and XO4
Authors: Tarasov V. P. , Privalov V. I. , Buslaev Yu. A. , Eichhoff U.
Published: February 2015

Changes in X-nuclei screening and scalar spin-spin X-H(D) coupling constants induced by the H-D substitutions in isotopomers [XH4-nDn] (X = N, Al, Ga) have been determined by 14,1l5N, 27 AI, 69,71Ga NMR. Isotopic chemical shifts of nuclei 51V, 53Cr, 99Tc induced by the 16O-18O substitution have been measured for tetra-oxo complexes [VO4]3-, [CrO4]2-, and [TcO4]-. The deuterium-induced secondary isotopic effect on the screening constant of the X nuclei and the scalar spin-spin X-H(D) coupling are correlated with the X-H bond length in [XHJ for the row X = N, C, B, Al, Ga, As the internuclear X-H distance increases, the isotopic shift of the X nuclei with respect to the signal from [XHJ rises linearly on H-D substitution from a negative value for [NH4]+, CH4 to a positive value (the downfield shift) for [GaH4]-. When D is substituted for H in [XH4] the X-H spin-spin coupling constant decreases for X = N, C, B, Al, Ga (the secondary isotopic effect). The magnitude and sign of the secondary isotopic effects on the screening constants of the X nuclei in [XH4] and [XO4] depend on the atomic number of the X element. With the increasing atomic number in the period the isotopic shift to high field rises in magnitude, while with the increasing atomic number in the group the isotopic upfield shift drops in the absolute value and can even change sign in the substitution of the ligand light isotope by a heavier isotope.
Das Redoxsystem Eisen/Iod: Untersuchungen in Acetonitril und Tetrahydrofuran. Eine neue Synthese für Tetraiodoferrat(III) / The Redox System Iron/Iodine: Investigations in Acetonitrile and Tetrahydrofuran. A Novel Synthesis of Tetraiodoferrate(III)
Authors: Pohl Siegfried , Saak Wolfgang
Published: February 2015

The oxidation of iron by iodine in acetonitrile and tetrahydrofuran solution leads to specific redox equilibria. In dependence of the molar ratios of Fe and I2 the following compounds are isolated: Fe(CH3CN)6Fel4, Fe(CH3CN)6(I3)2, Fe(C4H8O)6[FeI3(C4H8O)]2.

When Et4NI is added to a tetrahydrofuran solution of FeI2 and I2, Et4NFeI4 can be obtained Evidence is presented for the stability of Et4NFeI4 to autoreduction.

A resonance Raman spectrum has been obtained for Et4NFeI4. Crystal data for the different compounds are reported.
Investigations of Boranediylation and Exchange Reactions of Some 1,2-Dihydroxy / Compounds and their O-Organylboranediyl Derivatives Using 18O and 10B Isotopically Labelled Triethylboroxines
Authors: Yalpani Mohamed , Schmöller Wulf , Henneberg Dieter
Published: February 2015

The boranediylation of dihydroxy compounds and exchange reactions involving R-B-O groups of a number of their O-boranediyl derivatives with 18O and 10B labelled triethylboroxines has been investigated. It has been found that in simple 1,2-dihydroxy compounds only the RB group is substituted or exchanged. In hydroxy compounds such as ninhydrin 7 and octahydroxy- cyclobutane 6 both RB and RBO groups are involved. The mechanisms of these exchange reactions arc discussed.
Phosphaniminatokomplexe von Molybdän / Phosphaneiminato Complexes of Molybdenum
Authors: Schmidt Inge , Kynast Ulrich , Hanich Jürgen , Dehnicke Kurt
Published: February 2015

We report the syntheses and IR spectra of phosphanciminato complexes of molybdenum:

(MoVCl4(NPPh3)(PPh3)] (I)

PPh4[MoIVCl4(NPPh3)(PPh3)] · 2CCl4 (II)

PPh4[MoVCl5(NPCl3)] (III)

I is obtained from [MoNCl4]2 and triphenylphosphane, or from [MoCl4(NSCl)]2 and triphenylphosphane: II was prepared by reacting MoNCl4 with triphenylphosphane followed by treatment with tetraphenylphosphonium chloride; III can be generated from PPh4[MoNCl4] with PCl3/PCl5. Complex I is paramagnetic (μeff, = 1.83 B.M., d1-configuration): II is diamagnetic (d2-system).
Darstellung und Struktur von Chloroarsenaten(III) organischer Stickstoffbasen / Preparation and Structures of Chloroarsenates(III) of Organic Nitrogen Bases
Authors: Kaub J. , Sheldrick W. S.
Published: February 2015

The chloroarsenates(III) N-Methylanilinium-tetrachloroarsenate(III) (1). tris-pyridinium- nonachloro-diarsenate(III) (2) and bis-pyridinium-μ-dichloro-μ-oxo-tetrachlorodiarsenate(111) (3) have been prepared, the latter by partial hydrolysis of 2. Their structures have been determined by X-ray structural analysis and shown to contain discrete As2Cl8
2- (1), As2Cl9
3- (2) and As2Cl6O2- (3) anions. Pseudo-octahedral coordination is observed for the As-atoms in 1 and 3. The anion dimensions and the absence of chain building for anions 1 and 3 are in accordance with a markedly weaker acceptor strength of AsCl3 in comparison to SbCl3.
The Role of Reactive Oxygen Species in the Light-Induced Deformation of DNA
Authors: Baumann R. , Herrmann M. , Parlar H.
Published: February 2015

Dimerizations and reactions with water of pyrimidine bases are the primary steps held respon­sible for the deformation of DNA at short wavelengths in vitro and in vivo experiments. However the influence of oxygen in combination with water on the UV deformation at wavelengths rep­resentative for troposphere is evident from the observed data and both together are needed to change the DNA structure. The only plausible explanation for the effect of oxygen is the forma­tion of reactive oxygen species during the UV irradiation of DNA. In the present work the deformation of DNA by different oxygen species like singlet oxygen (1O2), superoxideanion (O2
-), hydroxyradical (·OH), ozone (O3) and hydrogenperoxide (H2O2) is excluded with the help of chemical-trapping experiments. The photo-induced transformation proceeds via excited states of DNA. which react with groundstate oxygen to afford peroxide.
Isolation of Seven Verrucosane Diterpenoids from the Liverwort Scapania bolanderi
Authors: Matsuo Akihiko , Atsumi Kazunori , Nakayama Mitsuru
Published: February 2015

From the liverwort Scapania bolanderi eight kinds of diterpenoids have been isolated together with two kinds of sesquiterpenoids, and seven of them have been identified as the verruconsane and neoverrucosane diterpenoids with 3,6,6,5-tetracyclic carbon framework.
Photoreactions of 3,5-Diaryl-and 5-Phenyl-3-styryl-2-cyclohexen-1-ones
Authors: Afsah E. M. , Elzahab M. M. Abou , Zimaity M. T. , Proctor G. R.
Published: February 2015

Photodimerization of 3,5-diaryl-2-cyclohexenones (1) in benzene solution gave the dimers 3. “Head-to-tail” structures are assigned for 3 on the basis of spectroscopic studies and reasoning from molecular models. Photolysis of the 3-styryl derivatives (5) afforded bicyclo[4,2,0]octan-1,5-dienes (8).
Notizen: Isolation and Structure of Rosamine a New Pseudoindoxyl Alkaloid from Catharanthus roseus
Authors: Atta-ur-Rahman  , Ali Irshad , Bashir M. , Iqbal M.
Published: February 2015

The isolation and structure of a new pseudoindoxyl alkaloid from Catharanthus roseus leaves is described.
Fluoride und Fluorosäuren, VIII [1]. Über eine fehlgeordnete feste Phase des SF4 sowie die Kristallstrukturen von Produkten seiner unbeabsichtigten Hydrolyse in Glasapparaturen, SiF4 (Neubestimmung) und SOF2 / Fluorides and Fluoro Acids, VIII [1]. On a Disordered Solid Phase of SF4 and the Crystal Structures of Products of its Unintentional Hydrolysis in Glass Apparatus, SiF4 (Redetermination) and SOF2
Authors: Mootz Dietrich , Korte Lutz
Published: February 2015

A structural investigation on single crystals of SF4 yielded the cubic space group Fm3m with a = 676.1(5) pm and Z = 4 and from this cubic close packing and at least sixfold disorder of isolated molecules. In one of the experiments of manipulating SF4 unintentional hydrolysis of the compound in a Duran-glass vacuum line occurred. The products SiF4 and SOF2 could be characterized by structure analysis after a miniature zone-melting separation and crystal growth in one and the same thin-walled capillary. The results for SiF4 [14̄3m, a = 547.6(1) pm, Z = 2 at -117 °C] confirm earlier work with a higher numerical accuracy. SOF2 crystallizes in the monoclinic space group P21/c with a = 524.7(1), b = 704.9(2), c = 1449.3(4) pm, β = 97.20(2)° at - 137 °C and Z = 8. Isolated molecules of pyramidal geometry are arranged in strongly folded layers with intermolecular S···O contacts.
Fluoride und Fluorosäuren, IX [1]. Verbindungsbildung im System NOF–HF sowie Kristallstrukturen von NOF·3 HF und NOF·4 HF / Fluorides and Fluoro Acids, IX [1]. Compound Formation in the System NOF–HF and Crystal Structures of NOF·3HF and NOF·4HF
Authors: Mootz Dietrich , Poll Wolfgang
Published: February 2015

The melting diagram of the system NOF-HF (HF-rich region) was studied by DTA and X-ray diffraction. The compounds NOF·3HF and NOF·4HF were confirmed as intermediate solid phases, and formation of a new one, NOF·7HF , was observed. The melting points are -1 °C (dec.), 5 °C and -106 °C (dec.), respectively. The crystal structures of NOF·3HF (space group R3c ,Z = 6 , a = 7.396 Å , c = 12.678 Å) and NOF·4HF (141/a, Z = 4, a = 6.316 Å , c = 13.301 Å) were determined as those of nitrosonium hydrogen fluorides, NO[F(HF)3] and NO[F(HF)4], with orientational disorder of the cations and very strong F-H···F hydrogen bonds in the anions.