bluuebunny/crossref_metadata_2025 huggingface dataset:
Housing policy in Scotland since devolution: divergence, crisis, integration and opportunity
Authors: Gibb Kenneth
Published: February 2015

Housing policy in Scotland is both distinctive and largely though not wholly devolved. Since 1999, housing has been at the core of divergent policymaking. In the recent referendum period, housing also featured indirectly in terms of the housing-related impacts of welfare reform such as the bedroom tax. Consequently, the proposed changes devolving aspects of welfare and borrowing proposed by the Smith Commission also have ramifications for housing. However, continuing housing need in Scotland and the various challenges identified in this paper to achieving strategic policy goals for the housing system mean that housing will remain a priority.
Contextualising Social Work Education in India
Authors: Adaikalam Francis, V.
Published: February 2015

Professional Social Work Education is commemorating 75 years of its contribution in addressing social problems and social welfare in India. While engaging layers of social realities, social work tries to create academic rigour, tests out new models and demands a statutory professional regulatory system. This article provides an overview on the issues, challenges and concerns of social work education in India. The first part details the historical development, the second part brings out various debates, the third part discusses the future concerns and challenges for social work education in India and it ends with a discussion.
Editorial: La Comunicación ¿al final de la crisis?
Authors: Tur-Viñes Victoria
Published: February 2015

Inauguramos el sexto año (V6) de publicación ininterrumpida de Revista Mediterránea de Comunicación con un ajuste importante en las fechas de publicación de los números semestrales. Adelantamos su publicación al principio de cada semestre, esto es, enero y julio. El objetivo es ganar tiempo de exposición en el año natural, aspecto que favorece los cálculos de algunos indicadores de impacto. Durante este año también queremos intensificar la presencia de la revista en bases de datos, primer paso del plan estratégico de comunicación previsto.
Redes sociales, popularidad e influencia social. El caso de la ciberprotesta contra la Ley de Telecomunicaciones en México, 2014
Authors: Torres Nabel Luis César
Published: February 2015

El artículo discute dos hipótesis sobre la influencia social que se ejerce en las redes sociales de Internet. La discusión se centra en el poder de la popularidad y la posición de los activistas políticos a la hora de protestar en un medio cibernético como twitter. El caso analizado es el de la ciberprotesta contra la ley de telecomunicaciones en México en 2014. Entre las conclusiones del estudio se destaca el efecto de la popularidad en las redes sociales como estrategia para la promoción de los conflictos que detonan el contagio de ideas y tendencias en la red. Una tesis muy similar a la propuesta por Manuel Castells sobre los programadores de la red, actores sociales que gracias a su posición y jerarquía tienen una serie de recursos y ventajas.
Repensar la publicidad local en tiempos de crisis
Authors: González Esteban José Luis
Published: February 2015

Durante los últimos años se han realizado numerosos estudios analizando la crisis de la prensa tradicional en España y aportando claves, más o menos acertadas, para su necesaria reinvención. La crisis global, unida a una crisis del sector prensa, ha golpeado duramente a uno de los eslabones más débiles, pero a la vez más necesarios: el periodismo de proximidad. Tal es así que en el ecosistema mediático local que analiza este libro se han producido cambios traumáticos en muy poco tiempo. En este sentido, cabe destacar el caso de uno de los medios investigados por la autora: el diario La Verdad. Cuando se inicia esta investigación, Vocento, empresa propietaria de La Verdad de Murcia, todavía mantenía las ediciones de Albacete y Elche (fundadas en los años setenta del pasado siglo) y Alicante. A día de hoy, la única edición que ha sobrevivido a la crisis es la de Alicante que por otra parte es uno de los objetos de estudio de este libro, junto con el diario Información, líder en esta provincia y propiedad del grupo Prensa Ibérica.
Experimental investigation of dispersion phenomenon in a fractured porous medium
Authors: Sanati Ali , Yousefi Khoshdaregi Mohammad
Published: February 2015

Dispersion of fluids flowing through porous media is an important phenomenon in miscible displacement. Dispersion causes instability of miscible displacement flooding; therefore, to obtain and maintain the miscibility zone, the porous medium dispersivity should be considered in displacing fluid volume calculation. Many works have been carried out to investigate the dispersion phenomenon in porous media in terms of theory, laboratory experiments and modeling. What is still necessary is to study the effects of presence of fracture in a porous medium on dispersion coefficient or dispersivity. In this work dispersion phenomenon in a fractured porous medium has been investigated through a series of miscible displacement tests on homogeneous sandstone core samples. Tests were repeated on the same core samples with induced fracture in the flow direction. The effects of fracture on miscible displacement flooding have been studied by comparison of the results of dispersion tests in the absence and presence of fracture. In the presence of fracture, breakthrough time reduced and the tail of effluent S-shaped curve smeared. Moreover, the slope of S-shaped curve at 1 pore volume of injected fluid was lower than homogeneous case which means dispersion coefficient increased. The results presented in this work provide an insight to the understanding of dispersion phenomenon for modeling of miscible displacement process through naturally fractured reservoirs.
Polypyrrole-Coated Jute Substrate for Electromagnetic Shielding
Authors: Khare Shalu , Deogaonkar Smita C. , Savadekar Niranjan
Published: February 2015

In this study, electrically conductive polypropylene (PP) and jute nonwoven fabrics were synthesized by a chemical oxidative polymerization process using pyrrole as a monomer and iron chloride hexahydrate as an oxidant. After fabric production, electrical, morphological, and electromagnetic properties were determined. The deposition of polypyrrole (PPy) on nonwoven fabrics was confirmed by scanning electron microscopy (SEM) analysis. Electrical properties were evaluated as surface resistivity using two probe flat plate electrode systems. The electromagnetic interference shielding of PPy-coated fabrics (PP and jute nonwovens) and composites was measured as shielding effectiveness (SE) in the frequency range of 100 MHz to 1.5 GHz using the co-axial transmission line method.
Reevaluation of AATCC Test Method 66: Dynamic Measurement of Wrinkle Recovery
Authors: Junfeng Tan , Lei Wang , Jianli Liu
Published: February 2015

AATCC Test Method (TM) 66 is a widely used method to determine wrinkle recovery of woven fabrics. Using a dynamic measurement system designed in the author's laboratory, this study enabled dynamic measurement of every frame image collected during the wrinkle recovery process. The precision of this system was tested against a standard wrinkle recovery angle tester. Data and plot comparisons indicated that the wrinkle recovery period in AATCC TM 66 should be shortened to balance both efficacy and efficiency.
Pharmacogenetics of drug oxidation via cytochrome P450 (CYP) in the populations of Denmark, Faroe Islands and Greenland
Authors: Brosen Kim
Published: February 2015

Denmark, the Faroe Islands and Greenland are three population-wise small countries on the northern part of the Northern Hemisphere, and studies carried out here on the genetic control over drug metabolism via cytochrome P450 have led to several important discoveries. Thus, CYP2D6 catalyzes the 2-hydroxylation, and CYP2C19 in part catalyzes the N-demethylation of imipramine. The phenomenon of phenocopy with regard to CYP2D6 was first described when Danish patients changed phenotype from extensive to poor metabolizers during treatment with quinidine. It was a Danish extensive metabolizer patient that became a poor metabolizer during paroxetine treatment, and this was due to the potent inhibition of CYP2D6 by paroxetine, which is also is metabolized by this enzyme. Fluoxetine and norfluoxetine are also potent inhibitors of CYP2D6, and fluvoxamine is a potent inhibitor of both CYP1A2 and CYP2C19. The bioactivation of proguanil to cycloguanil is impaired in CYP2C19 poor metabolizers. The O-demethylation of codeine and tramadol to their respective my-opioid active metabolites, morphine and (+)-O-desmethyltramadol was markedly impaired in CYP2D6 poor metabolizers compared to extensive metabolizers, and this impairs the hypoalgesic effect of the two drugs in the poor metabolizers. The frequency of CYP2D6 poor metabolizers is 2%–3% in Greenlanders and nearly 15% in the Faroese population. The frequency of CYP2C19 poor metabolizers in East Greenlanders is approximately 10%. A study in Danish mono and dizygotic twins showed that the non-polymorphic 3-N-demethylation of caffeine catalyzed by CYP1A2 is subject to approximately 70% genetic control.
Darstellung und Charakterisierung substituierter Phosphinoether und -thioether / Preparation and Characterization of Substituted Phosphinoethers and -thioethers
Authors: Wolfsberger Werner , Burkart Wolfgang , Werner Helmut
Published: February 2015

The (diorganophosphinopropyl)alkyl ethers 1-7 are prepared by hydrophosphination of allylalkyl ethers with secondary phosphines. The corresponding thioethers cannot be obtained in a pure state by the same route. The nucleophilic ring opening of thiirane with lithium dialkyl phosphides, followed by the reaction with ClSi(CH3)3 or Cl(CH2)2OCH3 produces the thioethers 8-12 and 16. The silylated thioethers 8, 10 and 12 react with CH3OH/H2O to give the phosphinoethyl thiols 13-15. All new compounds have been identified and characterized by elemental analyses, IR and NMR spectra.
Dy3Co6Sn5 – a New Stannide with an Ordered La3Al11 Type Structure
Authors: Pöttgen Rainer
Published: February 2015

The title compound has been obtained by arc-melting of the elemental components and subsequent annealing at 800 °C. It crystallizes in the orthorhombic space group Immm, a = 430.3(1), b = 1235.0(2), c = 967.6(3) pm, V = 0.5142(2) nm3, Z = 2. The structure has been determined from single-crystal X-ray data and refined to R = 0.0181 for 747 F2 values and 28 variables. It is of a new type and can be described as a ternary ordered version of the binary La3Al11-type structure. Dy3Co6Sn5 is built up from DyCo2Sn2 and DyCo2Sn slabs with ThCr2Si2 and Cu3Au-like atomic arrangements, respectively. Its crystal chemistry is compared with that of structurally related rare earth transition metal gallides.
Kristallstruktur von (CO)5CrPH2COOH und ab initio-Berechnung des hypothetischen freien Liganden [H2PCOOH]2 – ein Vergleich / Crystal Structure of (CO)5CrPH2COOH and ab initio Calculation of the Hypothetical Free Ligand [H2PCOOH]2 – a Comparison
Authors: Diemert Klaus , Hahn Thomas , Kuchen Wilhelm , Mootz Dietrich , Poll Wolfgang , Tommes Peter
Published: February 2015

Crystal structure analysis of (CO)5CrPH2COOH (a = 1338.2, b = 622.6, c = 1161.5 pm, β = 96,77°, P21/c, Z = 4, R = 0.0330) has shown the complex to be dimerized via hydrogen-bonds of the COOH group. Geometrical parameters of the hypothetical free ligand [H2PCOOH]2 were calculated using the HF/3-21 G*, HF/6-31G** and MP2-FU/6-31 G** basis sets. Bond lengths and bond angles of the calculated free ligand are similar to those derived from the crystal structure analysis of the coordinated ligand and are not significantly influenced by coordination and/or intermolecular interactions.
Synthese und Kristallstruktur eines Oxoantimonats mit Verwandtschaft zum Delafossit-Typ: Cu3MgSb1,4O6/Synthesis and Crystal Structure of an Oxoantimonate with Relationship to the Delafossite Type: Cu3MgSb1,4O6
Authors: Szillat H. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of Cu3MgSb1.4O6 have been prepared by crystallization from melts and investigated by X-ray diffractometer techniques. Cu3MgSb1.4O6 crystallizes trigonally, space group C3v
6 - R3/c, a = 5.348(1), c = 34.482(8) A, Z = 6, with a Delafossite related new structure, characterized by layers containing SbO6 and MgO6 octahedra. These layers are connected by O-Cu-O dumb-bells. The crystal structure is discussed with respect to the Delafossite type.
A Regioselective One Pot Synthesis and Synthetic Applications of Cyanodeoxy Sugars by Cyanotrimethylsilane
Authors: Kazmia Syed Najam-ul-Hussain , Ahmed Zaheer , Malik Abdul , Afza Nighat , Voelterc Wolfgang
Published: February 2015

The regioselective epoxide opening of different 2,3-anhydropyranoses by cyanotrimethylsilane is investigated. The isolated cyanodeoxy pyranoses allow easy access to the corresponding branched-chains aminomethyl sugars by lithium aluminium hydride reduction or sugar amides by controlled acid hydrolysis.
Systematic Structural Investigations on Phosphines
Authors: Bruckmann Joachim , Krüger Carl , Lutz Frank
Published: February 2015

This work contributes to the systematic investigation of phosphines. In an attempt to determine the nature, shape, volume and direction of the lone pairs at the phosphorus atoms in phosphines, high resolution X-ray structure analyses of triphenylphosphine, tris(p-methoxyphenyl) phosphine, bis(2,4,6-triisopropylphenyl)phosphine, 1,1 -bis(diphenylphosphino)ethene and 4,5,6-triphenyl-4-phosphaspiro[2.4]hept-5-en have been carried out. New valence force field param eters (TRIPOS force field) are presented which were developed on the basis of the molecular structures of the free phosphines. The results of crystal growing experiments using zone melting techniques are summarized.
Tetrabutylammonium Salts of 2-Nitropropane, Cyclopentadiene and 9-Ethylfluorene: Crystal Structures and Use in Anionic Polymerization
Authors: Reetz Manfred T. , Hütte Stephan , Goddard Richard
Published: February 2015

Reaction of the CH-acidic compounds 2-nitropropane, cyclopentadiene and 9-ethylfluorene with HON (nBu)4 affords the corresponding tetrabutylammonium salts in crystalline form, which have been characterized by X -ray structure analysis. The nitrostabilized salt is not a “naked ” anion (real carbanion). Rather, the α-methylene entities of the N+(nBu)4 cations form relatively strong hydrogen bonds with the O -atom s of the nitronateanion, forming dimers in a three-dimensional network. In solution dimers in the form of supramolecular ion pairs exist. In contrast, the cyclopentadienyl anion appears to be a real carbanion, since anion and cation do not interact with one another via H -bonding. The structure of the N+(nBu)4 salt of the 9-ethylfluorenyl anion is a special case in that closer contacts between cation and anion occur, which may be indicative of unusual [CH ··· C]- bonding. All three salts function as initiators in the metal-free anionic polymerization of acrylates and methacrylates at room temperature. In the case of tetrabutylammoniumcyclopentadienide, star polymers are formed.
Problems in Selective Catalysis with Molecular Imprints in Silica - Selective Lactones Formation from Hydroxyesters in Micropores -
Authors: Heilmann Jens , Maier Wilhelm F.
Published: February 2015

Selective lactone formation from hydroxy esters can be obtained with microporous glass catalysts. By a sol-gel polycocondensation of TEOS and a cyclic phosphonate an imprinted microporous silica catalyst was prepared. The imprint molecule selected is a transition state analogue for the lactone formation from hydroxy esters. Although selective γ- and δ-lactone formation from the respective hydroxy esters was observed, control experiments revealed, that the catalytic selectivity of the lactone formation is already obtained by the micropores of the material and not associated to the imprint. The study illustrates the importance of proper control experiments for the evaluation of imprint effects in selectively catalyzed reactions.
[TiH2 · (MgCl2 · 2 THF)0.2 – 0.3] – der naßchemische Weg zu einem hochreaktiven Titanhydrid / [TiH2 · (MgCl2 · 2 THF)0.2 – 0.3] -the Wet Chemical Route to a Highly Reactive Titanium Hydride
Authors: Becker Beate , Bogdanović Borislav
Published: February 2015

The reaction between catalytically prepared magnesium hydride (MgH2*) and [TiCl3(THF)3] in a molar ratio of 1.5:1 in THF yields a highly pyrophoric, X -ray amorphous titanium hydride precipitate with the composition [TiH2 ·(MgCl2 · 2 THF)0.2 - 0.3] (2). This novel titanium hydride has been characterized through hydrolysis and iodolysis, as well as through thermolysis to Ti* and H2 in the solid state and in organic solvents. 2 is slightly soluble in THF and proves itself as an active reagent in a variety of reactions.
Bonding in Cyclobutabenzene Chromium Tricarbonyl Complexes Studied by 13C NMR. Evidence of π-Bond Localization from 1J(13C,13C)
Authors: Butenschön H. , Gabor B. , Mynott R. , Wey H. G.
Published: February 2015

The 13C NMR parameters of several cyclobutabenzenes ( 1a - 1e ) and their corresponding complexes (cyclobutabenzene)M(CO)3 (M = Cr, Mo, W, 2 - 4 ) are presented and discussed. Two cyclobutabenzenes 1b and 1d and their chromium tricarbonyl complexes 2b and 2d have been examined in greater detail: the signal assignments have been confirmed by 2 D-INADEQUATE and the one bond coupling constants 1J(13C ,13C) measured at natural abundance using 1 D-INADEQUATE . Although the results provide no insight into why the chromium complex of 1,2 - dioxocyclobutabenzene (1e) is much more reactive at the keto groups than 1e itself, they do reveal a weak but not negligible alternation of the carbon s-character in the C - C bonds of the 6-membered rings both in the free cyclobutabenzenes and in the complexes, thus providing evidence for slight bond fixation (Mills-Nixon effect).
Molecular Modelling: Ein Beitrag zum Verständnis der katalytischen enantioselektiven Hydrovinylierung von Styrol / Molecular Modelling: A Contribution to the Understanding of the Catalytic Enantioselective Hydrovinylation of Styrene
Authors: Angermund Klaus , Eckerle Anette , Lutz Frank
Published: February 2015

The hydrovinylation of styrene can be catalyzed by the addition of phosphane-modified Ni(II) compounds with high reactivity and enantioselectivity if the azaphospholene 1 is used as P-component of the catalysts. Until recently the industrial applications of 1 have been hampered by its difficult synthesis. To search for easier to synthesize, but equally well catalyzing derivatives of 1 a molecular modelling study was carried out. Based on already experimentally tested and structurally characterized azaphospholenes a model is developed, which not only leads to a better understanding of the catalytic process and but also to a relatively easy way to predict catalytic properties in these systems. Using an extended, customized valence force field several new derivatives of 1 have been tested. Their predicted and experimentally determined catalytic properties are in good agreement. The X-ray structures of the phenyl-substituted, monomeric azaphospholene 13, which hitherto results in the second best catalyst, and of its precursor 19 are presented.
The Reaction of Dienes with [Fe(Pri
2P(CH2)nPPri
2)] Species
Authors: Gabor B. , Goddard R. , Holle S. , Jolly P. W. , Krüger C. , Mynott R. , Wisniewski W.
Published: February 2015

The structure of the compounds formed upon reacting Fe(Pri
2P(CH2)nPPri
2)Cl2 (n = 1-3) and active-Mg with acyclic and cyclic 1,3-, 1,4- and 1,5-dienes depends upon the nature of the diene and upon the length of the methylene-chain bridging the two P-atoms of the bidentate ligand. For example, isoprene reacts to give either (η4-isoprene)2FePPri
2C2H4PPri
2 or (η4-isoprene)Fe(Pri
2PC3H6PPri
2) while the products of the reaction with 1,5-hexadiene are (η5-1-methylpentadienyl)Fe(Pri
2PC2H4PPri
2)H or (η2,η2-1,5-hexadiene)Fe(Pri
2PC3H6PPri
2). The crystal structures of the last two compounds have been established by X-ray diffraction. The penultimate species catalyses the linear dimerization of 1,5-hexadiene.
Charge Transfer Photochemistry of Bis(8-quinolinolato)copper(II) and Bis(8-quinolinethiolato)copper(II) in Aprotic Solvents
Authors: Jeliazkova Bojana G. , Panajotova Julia K.
Published: February 2015

The photochemistry of bis(8-quinolinolato)Cu(II), Cu(ox)2, and bis(8-quinolinethiolato)- Cu(II), Cu(tox)2, has been studied by continuous photolysis in aprotic solvents. The charge transfer irradiations induce the oxidation of the ligand and the reduction of copper(II) to copper(I). These assignments are supported by EPR data and UV-Vis spectra of the complexes. The photochemical properties of copper(II) complexes are discussed in terms of the population of charge transfer to copper-excited states. Both complexes show solvent-dependent photochemistry when irradiated in CHCl3 and in toluene. The photoproducts of Cu(tox)2 in CHCl3 are partially reconverted into the initial complex by thermal reaction, while photoreactions of Cu(ox)2 lead to secondary photolytic processes.
4- and 5-Coordinate Dinuclear Copper(II) Complexes with the Tetraacetylethanediide and an N-Alkylated Diamine or a Triamine
Authors: Kambayashi Hide , Yuzurihara Junko , Masuda Yuichi , Nakagawa Hiroko , Linert Wolfgang , Fukuda Yutaka
Published: February 2015

Six dinuclear copper(II) complexes have been prepared, Cu2(taet)(plam)2X2 where taet = 1,1,2,2-tetraacetylethanediide, plam = N-alkylated polyamine such as tmen = N,N,N′,N′-tetramethylethylenediamine or pmdt = N,N,N′,N′,N′-pentamethyldiethylenetriamine, X = a monovalent anion such as ClO4
- , NO3
- or Cl-. These complexes are classified into two categories from the results of electronic spectra, IR spectra, and X-ray single crystal structure analysis as follows: (1) 4-coordinate-4-coordinate dinuclear, [Cu2(taet)(tmen)2]X2 (where X = ClO4
- or NO3
-), (2) 5-coordinate-5-coordinate dinuclear, [Cu2(taet)(tmen)2Cl2], and [Cu2(taet)(pmdt)2]X2 (where X = ClO4
-
, NO3
- , or Cl- ). The crystal structure of Cu2(taet)(tmen)2(ClO4)2 · H2O (1) has been determined by the single crystal X-ray diffraction technique; monoclinic space group P21/a with a = 26.478(3), b = 8.744(1), c = 15.601(3) Å, β = 106.195(9)°, and V = 3468.9(8) Å3 for Z = 4. The final agreement factors are R = 0.097 ( Rw = 0.099). The geometry of each Cu(II) moiety in the dinuclear cation (1) is 4-coordinate square planar with a N2O2 donor set. This tmen-dinuclear complex exhibits a very weak C u (II)-Cu (II) interaction (J = -0.5 cm-1), and shows characteristic ESR spectra with seven hyperfine peaks in 1,2-dichloroethane solution at room temperature. This is not found for the corresponding pmdt-dinuclear complex. All complexes obtained in this study are very soluble in many organic solvents. The tmen-dinuclear complexes show pronounced solvatochromic behavior-dependent on the solvent donor properties. This is not found for the corresponding pmdt-dinuclears, which are stable as 5-coordinated species.
Synthesis of [1,2,4,3]Triazaphospholo[1,5-a]pyridines+
Authors: Bansal Raj K. , Gandhi Neelam , Schmidpeter A. , Karaghiosoff K.
Published: February 2015

Condensation of 1,2-diaminopyridinium iodides with tris(dimethylamino)phosphine gives [1,2,4,3]triazaphospholo[1,5-a]pyridines 2a - d . Diethylamine adds to the N=P bond of 2a, b only if the phosphorus is oxidized at the same time. Hydrolysis of 2a opens the triazaphosphole ring at its 2,3-bond.
Iron(III)Porphinate/H2O2-Mediated Conversion of All-(E)-Retinol
Authors: Waldmann Doris , König Thorsten , Schreier Peter
Published: February 2015

The reaction of hydrogen peroxide with all-(E)-retinol (1) catalyzed by (meso-tetraphenylporphinato) iron(III) led to the formation of 4-hydroxyretinol (2), 4-oxoretinol (3), 5,8-epoxyretinol (4), 5,6-epoxyretinol (5), 3-dehydroretinol (6), all-(E)- and 12-(Z)-retroretinol (7/7a) as well as all-(E)- and 12-(Z)-anhydroretinol (8/8 a) as major non-volatile products. The conversion products were characterized by comparison of their chromatographic (HPLC) and spectroscopic data (UV; MS; 1H and 13C NMR) with those of synthesized reference compounds. The observed product formation supports the hypothesis of a C4 centered radical as the key intermediate of all-(E)-retinol conversion.
Wechselwirkungen in Kristallen, 63 [1, 2] Kristallisation und Strukturbestimmung von 1,2-Dimesitoylbenzol und von Bis(hydrogen-1,2-dimesitoylbenzol)-dinatrium-bis(ethylendiamin)/Interactions in Crystals, 63 [1, 2] Crystallization and Structure Determination of 1,2-Dimesitoylbenzene and of Bis(hydrogen-1,2-dimesitoylbenzene)-disodium-bis(ethylendiamine)
Authors: Bock Hans , Nick Sabine , Näther Christian , Bensch Wolfgang
Published: February 2015

Chelate complexes of 1,2-dimesitoylbenzene radical anion with alkali metal cations exhibit in aprotic solution extremely large ESR /ENDOR metal coupling constants. For rationalization, structures of both the neutral molecule (H3C)3H2C6 - CO - C6H4 - CO - C6H2(CH3)3, in which the two carbonyl groups are twisted out of the benzene ring plane by dihedral angles of ± 3̄7̄°, and a sodium contact ion quadruple have been determined. One of the dimers [dimesitoylbenzeneH⊖ (Na⊕H2N H2C - CH2NH2)]2, although generated by Na metal mirror reduction of 1,2-dimesitoylbenzene in aprotic DME solution with added ethylendiamine for better electron transfer, surprisingly contains two 245 pm short (!) hydrogen bridges ⊖O ··· (H)O and in addition two solvation bridges e ⊖O ··· Na⊕(H2NH2C - CH2NH2) ··· O⊖. Results of MNDO calculations based on the experimental coordinates support the proposed concept.
Synthese und Koordinationschemie eines neuartigen Bistetrazols: Ein 1D-Metallopolymer durch Selbstorganisation koordinativ ungesättigter Zink(II)-M4onomere [1] / Synthesis and Coordination Chemistry of a New Bistetrazole: A 1D-Metallopolymer via Self-Assembly of Monomeric Zinc(II)-Buildingblocks
Authors: Saalfrank Rolf W. , Schobert Klaus , Trümmer Stefan , Wolski Alexander
Published: February 2015

The new bistetrazole 13 has been obtained by subsequent formation of the two heterocyclic units. In methanolic solution 13 reacts with zinc(II) acetate to yield the pseudo-meso-1 D-coordination polymer [ZnL2(MeOH)]n (n = ∞) 14. The structure of 14 was established by single crystal X-ray diffraction. The generation of the polymeric chain 14 is understandable, if intermediate formation of coordinatively unsaturated zinc(II) buildingblocks (Δ)-15 and (Λ)-15 is assumed. Alternating linkage of the self-complementary chiral monomers 15, across one cyanofunction each, leads to 14 with zinc being essentially octahedrally coordinated. Compared with polymeric compounds of similar bridging ligands, the Zn ··· N≡C-distance in 14 (225,7 pm) is short.
New Synthesis and Structure Determination of 13-Aza-4,4,8,8,12,12-hexamethyl-2,6,10-trioxatricyclo[7,3,1,05,13]tridecane
Authors: Kehagia Konstantina , Dömling Alexander , Ugi Ivar , Hiller Wolfgang , Riede Jürgen
Published: February 2015

A new 13-Aza-4,4,8,8,12,12-hexamethyl-2,6,10-trioxatricyclo[7,3,1,05,13]tridecane synthesis and the crystal structure are reported. It crystallizes in the monoclinic space group P21/n with a = 1201.9(1) pm, b = 1436.6(1) pm, c = 1726.2(2) pm, β = 90.74(1)° and Z = 8.
Synthesis of 3′-PEG -Modified Oligonucleotides on PS -PEG Tentacle Polymers
Authors: Bayer Ernst , Maier Martin , Bleicher Konrad , Gaus Hans-Joachim
Published: February 2015

PS-PEG tentacle polymers are modified for the synthesis of oligonucleotides covalently bound to polyethylene glycol (P E G ) at their 3′-position by the solid phase method without additional steps. The average stepwise coupling rates and overall yields are in the range of standard oligonucleotide synthesis. Oligonucleotides and phosphorothioates up to 20 nucleotides, modified with hexaethylene glycol (H E G ), PEG400 and PEG1500, are synthesized in this manner. The products are characterized by capillary electrophoresis and electrospray mass spectrometry (ES-MS). These new methods are very efficient for purity control as it is required for potential antisense drugs.
Notiz zur Kristallchemie von LiBa2Cu3O6 / Note on the Crystal Chemistry of LiBa2Cu3O6
Authors: Tams G. , Müller-Buschbaum Hk. , Lang Ch.
Published: February 2015

Single crystals of LiBa2Cu3O6 have been prepared by recrystallization from melts in a stream of dry Argon as well as by spontaneous CO2- LASER heating. It crystallizes with orthorhom bic symmetry, space group D23
2h - Fmmm, a = 8,219(2), b = 11,520 (2), c = 14,284(3) Å, Z = 8. The crystal structure is isotypic to NaBa2Cu3O6.
Notizen: Preparation of Dimeric [(η5-tBu3Cp)CoBr]2 and Convenient Synthesis of the Homodinuclear Cobalt Complex [(η5-tBu3Cp)Co]2H3 therefrom.
Authors: Schneider Jörg J. , Specht Ullrich
Published: February 2015

The title compound [(η5-tBu3Cp)CoBr]2 1 is prepared in a one pot reaction starting from 1,2,4- tBu3-cyclopentadiene followed by metallation and by reaction of the resulting tBu3Cp-K+ anion salt with anhydrous CoBr2 in THF. 1 was isolated from this reaction in 78% yield as black crystals. 1 reacts with LiAlH4 in THF at 0 °C. Subsequent alcoholysis of the crude reaction mixture with ethanol at -78 °C gives the novel trihydride cluster [(η5-tBu3Cp)Co]2H3 2 in 58% isolated yield as black crystals. 2 has been characterized by 1H NMR, ESR, MS, and IR spectroscopy, as well as by elemental analysis.
Notizen: Neue N,Si,O,C-Heteraphane - Synthese eines 16-gliedrigen Makrocyclus / New N,Si,O,C-Heteraphanes - Synthesis of a 16-Membered Macrocycle
Authors: Marcus Lothar , Klingebiel Uwe , Noltemeyer Mathias
Published: February 2015

Bis(fluorodiisopropylsilyl)amine [(Me2HC)2SiF]2NH (1) reacts with the disodium salt of catechole or the disodium salt of resorcinol in a molar ratio 1:1 to give the seven-membered heteraphane [HN(Me2HC)2SiO]2C6H4 (2) resp. the 16-membered heteraphane [HN(Me2HC)2SiOC6H4OSi(CHMe2)2]2 (3). The chain-like compound [(Me2HC)2SiFNHSi(CHMe2)2O]2C6H4 (4) is obtained by the reaction of 1 with disodium resorcinolate.
Notizen: Neue fluorhaltige Phosphorylide aus 6-Phenyl-3-pentafluorphenoxy-tetrafluorcyclohexa- 2,4-dien-1-on und Triphenylphosphan / Novel Fluorine-Containing Phosphorus Ylids from 6-Phenyl-3-pentafluorophenoxy-tetrafluorocyclohexa- 2,4-dien-1-one and Triphenylphosphane
Authors: Grobe Joseph , Van Duc Le , Wiese Hinrich , Krebs Bernt , Läge Mechtild , Kobrina Lioubov S.
Published: February 2015

The reaction of 6-phenyl-3-pentafluorophenoxy-tetrafluorocyclohexa- 2,4-dien-1-one (1) with one equivalent of triphenylphosphane leads to the spectroscopically detectable 5-phenyl-4-pentafluorophenoxy- 3,3,6,6-tetrafluoro-2-triphenylphosphoranylidene- 4-cyclohexen-1-one (2), which upon hydrolysis or reaction with hydroxyl groups of the glass surface yields 5-phenyl-4-pentafluorophenoxy- 6,6-difluoro-2-triphenylphosphoranylidene- 4-cyclohexene-1,3-dione (3). The structure of 3 was determined by NMR measurements and an X-ray diffraction study.
Notizen: Synthesis of 3-Amino-3-deoxy Sugars through Intramolecular Carbamate Cyclizations on a Neighbouring Oxirane Ring
Authors: Zarga Musa H. Abu , Al-Telb Taleb H. , Voelter Wolfgang
Published: February 2015

3-Amino-3-deoxy sugars [1] are essential substructures of a wide variety of biologically active natural products exemplified in aminocyclitols, [2] macrolides [3] or anthracyclin antibiotics [4], With this respect, the transformations of common and readily available carbohydrates are of special interest. In this communication we want to line out a short route for the incorporation of a vicinal cis hydroxyl-amino function in the pyranose moiety.
Metallorganische Synthesen mit freien Cyclopentadienyl-Radikalen, I. Zweikernige Carbonylnickel-Komplexe mit mehrfach alkylierten Cyclopentadienyl-Liganden / Metalorganic Syntheses with Free Cyclopentadienyl Radicals, I. Dinuclear Carbonyl Nickel Complexes with Alkylated Cyclopentadienyl Ligands
Authors: Sitzmann Helmut , Wolmershäuser Gotthelf
Published: February 2015

Cyclopentadienyl nickel complexes [(C5H2tBu3-1,2,4)Ni(M-CO)]2 (1) and [(C5HiPr4)Ni(μ-CO)]2 (2) have been synthesized from nickel tetracarbonyl and the corresponding lithium cyclopentadienide, and [(C5iPr5)Ni(μ-CO)]2 (3) has been obtained in high yield from nickel tetracarbonyl and the free pentaisopropylcyclopentadienyl radical. The crystal structure of 1 shows a complex on a crystallographic mirror plane with a bent Ni-C-Ni-C core whereas the crystal structure of 2 exhibits two independent planar molecules possessing crystallographic inversion symmetry.
Synthese und Kristallstruktur von Verbindungen des Typs CuM[B5O10] (M = Tm3+, Lu3+) / Synthesis and Crystal Structure of Compounds of the Type CuM[B5O10] (M = Tm3+, Lu3+)
Authors: Schaefer Jan , Bluhm Karsten
Published: February 2015

Single crystals of the compounds CuM[B5O10] (M = Tm3+(I), Lu3+(II) have been obtained by a B2O3 flux technique. Their structures are isotypic with CuTb[B5O10]. X-ray investigations on single crystals led to the space group C21
2v-Iba2 (Nr. 45); I: a = 622,0(2) pm; b = 844,7(1) pm; c = 1266,3(4) pm; Z = 4 and II: a = 618.4(1) pm; b = 845,9(2) pm; c = 1260,9(4) pm; Z = 4. The structure contains 1
∞[B5O10]5- chains that include twelve membered rings of boron and oxygen. Each ring consists of two tetrahedral BO4 and two planar B2O5 groups and is connected with neighboring rings via the BO4 units. M3+ (M = Tm3+, Lu3+) is eight-coordinated, while Cu2+ is hexa-coordinated by oxygen.
Darstellung, 11B-NMR- und Schwingungsspektren von μ-Amido-bis(hexahydro-closo-hexaborat)(1-), und Kristallstruktur von [As(C6H5)4][B6H6(NH2)B6H6] / Preparation, 11B NMR and Vibrational Spectra of μ-Amido-bis(hexahydro-closo-hexaborate)(1-) and Crystal Structure of [As(C6H5)4][B6H6(NH2)B6H6]
Authors: Franken A. , Preetz W.
Published: February 2015

By reduction of [B6H3(NO)B6H5]3- with Fe2+ in aqueous alkaline solution [B6H3(NH2)B6H3]3- is formed. It reacts as a Brönsted base and becomes protonated in neutral medium to give the mono anion [B6H6(NH2)B6H 6]-. The crystal structure of the salt [As(C6H3)4][B6H6(NH2)B6H6] has been determined by single crystal X-ray diffraction analysis; triclinic space group P1̄ with a = 8.284(2), b = 12.619(2), c = 15.5 4 3 (3 )Å and α = 69.193(13)°; β = 88.59(2)°, γ = 87.24(2)°. The 11B NMR spectrum is consistent with mono hetero substituted octahedral B6 cages with local C4v symmetry. The IR and Raman spectra exhibit characteristic N-H , B-H and B6 vibrations.
Übergangsmetallkomplexe mit Schwefelliganden, CVIII+. Eine bequeme Synthese des tertiären Amin-thiolat-Liganden 'S2N2Me2'2-. Einfluß der Aminmethylierung auf die Koordinationschemie von Nickel- und Ruthenium-Komplexen mit [M('S2N2R2')]-Geriisten (R = H, CH3). ('S2N2Me2'2- = 1,2-Ethandiamin-N,N'-dimethyl-N,N'-bis(2-benzolthiolat)(2-)) / Transition Metal Complexes with Sulfur Ligands, CVIII+. A Facile Synthesis of the Tertiary Amine-thiolato Ligand 'S2N2Me2'2-. Influence of the Aminomethylation on the Coordination Chemistry of Nickel and Ruthenium Complexes with [M('S2N2R2')] Frameworks (R = H, CH3). ('S2N2Me2'2- = 1,2-Ethanediamino-N,N'-dimethyl-N,N'-bis(2-benzenethiolato)(2-))
Authors: Sellmann Dieter , Ruf Richard , Knoch Falk , Moll Matthias
Published: February 2015

In a single pot synthesis consecutive reaction of the tetradentate amine-thiole H2-'S2N2H2' 2 ('S2N2H2'2- = 1,2-ethanediamino-N,N'-bis(2-benzenethiolato)(2-)). with [LiN(SiMe3)2] and benzyl chloride (BzCl) yields the amine-thioether 'Bz2S2N2H2' which gives the tertiary amine-thioether 'Bz2S2N2Me2' when reacted with further [LiN(SiMe3)2] and CH3I Removal of the benzyl groups with an excess of sodium and acidification with hydrochloric acid finally yield H2-'S2N2Me2' I ('S2N2Me2'2- = 1,2-ethanediamino-N,N'-di- methyl-N,N'-bis(2-benzenethiolato)(2-)). 1 and 2 have been characterized by X-ray structure analysis. With [Ni(CH3COO)2] · 4H2O,1 yields racemic [Ni('S2N2Me2')] 3 in a diastereospecific reaction. Crystallization of 3 leads to spontaneous resolution of the racemate. By X-ray structure analysis of 3 the absolute configuration in the single crystal examined was determi­ned using Roger's μ-refinement (μ = 1.00(4)). Upon reaction with [RuCl3·3H2O]. LiOMe and CO. I yields [Ru(CO)2('S2N2Me2')] 5. Spectroscopic data indicate that 5 and the parent complex [Ru(CO)2('S2N2H2')] differ with respect to their core structures. Influence of the amine methylation on structure and reactivity of complexes with [M('S2N2R2')] cores, R = H. Me, is discussed.
2-Stannylpyridine-Borane Adducts - Multinuclear Magnetic Resonance Study and X-Ray Structure Determination of a 1,4-Dihydro-4 a,1,4-azastannabora-naphthalene Derivative
Authors: Wrackmeyer Bernd , Maisel Heidi E.
Published: February 2015

The adduct formation between 2-trimethylstannyl-pyridine (1) and triethylborane, leading to 2a, and 9-borabicyclo[3.3.1]nonane, leading to 2b, was studied by 1H, 11B, 13C, 15N and 119Sn NMR in solution. Changes in the magnitude of the coupling constants J(119Sn, 13C), with respect to the data for I, were analysed. The absolute signs have been determined [all coupling constants nJ(119SnZ3C) to methyl and pyridine carbon atoms in 1 to 3 possess a negative sign and the same is true for nJ(119Sn,1H) of the pyridine hydrogen atoms] by various two-dimensional NMR experiments, and attributed to the influence of the lone pair of electrons at the nitrogen atom in 1. The NMR spectroscopic results for the 1,4-dihydro- 4a,1,4-azastannabora-naphthalene derivative 3, in which structural fragments are present analogous to those in the borane adducts 2, correspond to those for 1 and 2a,b. The molecu­lar structure of 3 has been determined by X-ray analysis [orthorhombic; P212121, a = 713.9(2), b - 1566.0(2), c = 1578.4(2) pm]. Solid-state 13C and 119Sn CP/MAS NMR spectra prove that the molecular structures of 3 in the solid state and in solution are very similar.
Kristallstrukturen zweier Kupfer(II)-Cyclam-Komplexe: [{CuCl(C10N4H24)}2][CdCl4] und [Cu(C10N4H24)][CdCl3(H2O)2]Cl / Crystal Structures of Two Copper(II) Cyclam Complexes: [{CuCl(C10N4H24 )}2][CdCl4] and [Cu(C10N4H24)][CdCl3 (H2O)2]Cl
Authors: Pickardt Joachim , Hoffmeister Isabella
Published: February 2015

Crystals of both complexes were obtained by evaporation of the ethanol solvent. The crystals of [{CuCl(C10N4H24)}2][CdCl4] are tetragonal, space group I4̄2d, Z = 4, a = b = 1784.1(11), c = 1101.1(8) pm. Each copper atom is bonded to one cyclam ligand and two chlorine atoms which are acting as bridging ligands and connect the copper atoms to chains of distorted octahedra. Distorted tetrahedra of CdCl4 are situated in cavities between these chains. The crystals of [Cu(C10N4H24)][CdCl3(H2O)2]Cl are monoclinic (b), space group C2/c, Z = 4, a = 1581.9(8), b = 1323.3(7), c = 924.0(5) pm, β = 94.31(5)°. Cadmium is coordinated to four chlorine atoms and two water molecules, while all of the chlorine atoms act as bridging ligands connecting every cadmium atom to two adjacent cadmium atoms and to two copper atoms which lie in plane with the N atoms.
Synthese und Kristallstruktur des 2.4-Di-terf-butoxy-2,4-di-terfbutylcyclodisilazans / Synthesis and Crystal Structure of 2.4-Di-terf-butoxy-2,4-di-terrbutylcyclodisilazane
Authors: Dielkus Sven , Großkopf Dorothee , Herbst-Irmer Regine , Klingebiel Uwe
Published: February 2015

Me3CSiHal3 react with LiOCMe3 to give Me3CO(Me3C)SiHal2 (HaI = F (1), Cl (3)). The aminofluorosilane, Me3CO(Me3C)SiFNH2 (2), is formed in the reaction of 1 with LiNH2. The diaminosilane Me3CO(Me3C)Si(NH2)2 (4) is obtained from the reaction of 2 with ammonia. 4 reacts with LiC4H9 to give the lithium derivative Me3CO(Me3C)Si(NHLi)NH2 (5). In a molar ratio 1:1 the reaction of 5 and 1 leads to the formation of the 1-amino-3-fluoro-disilazane Me3CO(Me3C)SiF- NH - SiNH2(CMe3)OCMe3 (6) and in a molar ratio 2:1 to the four-membered silicon nitrogen ring [Me3CO(M e3C)Si-NH]2 (7). The crystal structure of 7 was determined.
Kristallstrukturuntersuchung des Kupfer-Cadmium-Oxovanadats CuCdVO4 / Crystal Structure Investigation of the Copper Cadmium Oxovanadate CuCdVO4
Authors: Feldmann J. , Münchau S. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of CuCdVO4 have been prepared by CO2-LASER techniques. X -ray investigations of the black single crystals led to orthorhombic symmetry, space group D2h
17-Cmcm , a = 5.921(1), b = 9.065(4), c = 6.633(2) Å, Z = 4. CuCdVO4 represents the first example of a quaternary oxide containing cadmium and copper(I). Compared to AgCdVO4, CuCdVO4 shows a different linkage of the VO4 and CuO4 tetrahedra, explaining the missing isotypy of these com pounds.
Ein Silber- Kupfer - Oxovanadato-Oxomolybdat mit Silber in quadratisch-planarer Koordination: Ag0,5Cu3V0,5Mo2,5O12 / On a Silver Copper Oxovanadate-Oxomolybdate with Silver in Square Planar Coordination: Ag0,5Cu3V0,5Mo2,5O12
Authors: Szillat H. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of Ag0.5Cu3V0,5Mo2,5O12 have been prepared by crystallization from melts and investigated by X -ray methods. They crystallize with triclinic symmetry, space group Ci
1 -P 1̄ , a = 6.797(6), b = 8.575(6), c = 9.897(7) Å, α = 103.47(6), β = 103.69(6), γ = 101.48(6)° and Z = 4. The crystal structure is characterized by chains of edge-sharing CuO6 octahedra and CuO5 pyramids. Special features of this com pound are the square planar surrounding of Ag+ by O2− and a statistical distribution of molybdenum and vanadium at one point position.
β-P4S3-Hydride: Eine NMR-Untersuchung / β-P4S3-Hydrides: An NMR Study
Authors: Blachnik Roger , Hackmann Kerstin
Published: February 2015

β-Tetraphosphorus-trichalcogenide hydrides have been detected in the reaction mixtures of β-P4S3X2 (X = Cl, Br, I) with (CH3)3SnH in CS2 solutions. In the first step of the reaction the configuration of the hydrogen accepting phosphorus atom is inverted and the compound β-P4S3XexoHendo is formed, as the main product. Two further isomers β-P4S3ClexoHexo and β- P4S3HexoHendo w ere found in low concentrations.

The second nucleophilic substitution is slow and the configuration at the second hydrogenated phosphorus atom can be retain ed or inverted. Two products, β-P4S3HexoHendo and β -P4S3(Hendo)2, are observed.
Organosubstituierte 1,6,2,5-Azoniathiasilaboratabicyclo[3.3.0]oct-3-ene - Herstellung und Kristallstruktur / Organosubstituted 1,6,2,5-A zoniathiasilaboratabicyclo[3.3.0]oct-3-enes - Preparation and Crystal Structure
Authors: Köster Roland , Seidel Günter , Wrackmeyer Bernd , Boese Roland
Published: February 2015

The heterocycles

Et [R3 = Me: A; R3 = C(Me)=CH2: B] react with 2-aminoethanethiol (1) by elimination of MeNH2 to give the monocyclic

[R = Me: 3a; R = C(Me)=CH2: 3b] and the thermically more stable bicyclic compounds

[R = Me: 4a; R = C(Me)=CH2: 4b], 4a crystallizes in the monoclinic space group P21/c [lattice constants (at 120 K) a = 9.3239(10), b = 8.9225(11), c = 17.3958(23) Å; β = 92.207(9)°] with a folded bicyclic ring system. cis-ClB(Et)C=C(Me)Si(Me2)Cl (C) and Na2-1BEt3 (prepared from 1 and NaHBEt3) form by elimination of MeNH2 preferentially 3a and minor amounts of 4a. A reacts with o-aminothiophenol (2) via

(5) to

(6) and the products 7-10.
Notizen: Elektrochemische Darstellung von TlAg6O8ClO4 / Electrochemical Preparation of TlAg6 O8ClO4
Authors: Bilow Uta , Jansen Martin
Published: February 2015

TlAg6O8ClO4 has been synthesized for the first time by electrocrystallization. It is isostructural to silver clathrate salts like Ag7O8NO3, thus containing octacoordinated thallium(III) with d (Tl-O ) = 246 pm (Fm 3̄m , a = 1002.3(2) pm). The title compound shows temperature-independent paramagnetism, which appears to be caused by delocalization of unpaired electrons from Ag(II) into the conduction band.
Kristallstruktur des Quecksilber(II)-Cryptats [Hg(cryptand 222)][{Hg(SCN)3}2] mit einem kettenförmigen Tri(thiocyanato)mercurat(II)-Anion / Crystal Structure of the Mercury(II) Cryptate [Hg(cryptand 222)][{Hg(SCN)3}2] Containing a Tri(thiocyanato)mercurate(II) Anion with a Chain Structure
Authors: Pickardt Joachim , Gong Gill-Taik , Hoffmeister Isabella
Published: February 2015

The reaction of [2.2.2]cryptand, 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo- [8 .8 .8 ]hexacosane, with mercuric thiocyanate yields crystals of [Hg(cryptand 222 )][{Hg(SCN )3 }2]. The compound crystallizes monoclinically, space group C2/c, Z = 4, a = 2478.3(12), b = 1540.4(4), c = 1049.4(3) pm, β = 108.77(3)°. In the cation the mercury atom is 8 -coordinated by six oxygen and two nitrogen atoms with distances Hg -N 220(2) pm and Hg -O 268.8(9) pm (mean value). The polymeric anion consists of infinite chains -Hg -SCN -Hg - with bond distances Hg-S 254.2(4) and Hg-N 257(2) pm. Each Hg atom carries two additional terminal SCN ligands, with a mean Hg-S distance o f 244( 1) pm; the distance from Hg to the N atom of an SCN ligand of a neighbouring Hg atom is 300(2) pm, probably indicating an additional, although weak bonding.
Oligophosphan-Liganden, XXXIX. (1S,2S)-trans-Cyclopentan-1,2-diyl-bis(phosphan), C5H8(PH2)2, durch Reduktion eines diastereomerenreinen Cyclopentandiyl-bis(dioxaphospholans) / Oligophosphine Ligands, XXXIX. (1 S,2S)-trans-Cyclopentane-1,2-diyl-bis(phosphine), C5H8(PH2)2, by Reduction of a Diastereomerically Pure Cyclopentanediyl-bis(dioxaphospholane)
Authors: Eckert Christine , Dahlenburg Lutz , Wolski Alexander
Published: February 2015

The title compound (S,S)-2, has been obtained by reduction with Li[AlH4] of the cyclopentane- 1,2-diyl-bis(1′,3′,2′-dioxaphospholane) (1S ,2S)-trans-C5H8[P(OCH (CO2Pr-i)- (R) - )2]2, (S,S)-1, which itself was isolated in diastereomerically pure form (X-ray structure analysis) from the reaction between rac, trans-C5H8(PCl2)2 and (2R,3R)-(+)-diisopropyl tartrate. Cleavage of (S,.S)-1 withPCl3 yielded an unseparable mixture of (1S,2S)-trans-C5H8(PCl2)2 and (4R.5R) -ClP [OCH(CO2Pr-i)-]2.
Darstellung, 11 B-NMR- und Schwingungsspektren von cis-Dinitrotetrahydro-closo-hexaborat(2–), cis-[B6H4( NO2)2]2- sowie Kristallstruktur von cis-Cs2[B6H4(NO2)2] / Preparation, 11 B NMR and Vibrational Spectra of cis-Dinitrotetrahydro-closo-hexaborate(2–),cis-[B6H4(NO2)2]2-, and the Crystal Structure of cis-Cs2[B6H4(NO2)2]
Authors: Franken A. , Preetz W.
Published: February 2015

By electrochemical oxidation of [B6H6,]2 in the presence of nitrite ions and of the base DBU in dichloromethane solution apart from [B6H5 (NO2)]2- and [B6H5(NO)B 6H5]3- the dinitro anion cis-[B6H4( NO2)2]2- is formed and can be isolated by ion exchange chromatography on diethylaminoethyl cellulose. The crystal structure of the Cs salt has been determined from single crystal X-ray diffraction analyses. cis-Cs2[B6H4 ( NO2)2] is tetragonal, space group P4̄21 m with a = 10.0656(4), c = 11.0127(13) Å. The 11B NMR spectrum is consistent with a disubstituted octahedral B6 cage with local C2v symmetry. The IR and Raman spectra exhibit characteristic NO2, B - H and B6 vibrations.
Reactivity of an Arene Cobalt Triple Decker Complex Towards Various Ligands. Facile Arene Displacement in [Bis{( η5-pentamethylcyclopentadienyl)cobalt}-μ-{η4: η4-toluene}]
Authors: Schneider Jörg J.
Published: February 2015

The triple decker complex [{(η5-Cp*)Co}2-μ-{η4: η4-toluene}] 1b exhibits an unusual reactivity towards a variety of organic ligands, 1b reacts with CO, ethene, butadiene, H2, Al2O3, hexafluorobenzene, 1.5 Cod, 2-butyne, phenanthrene, naphthalene and the dinuclear Ni cluster [{(η5-Cp)NiP(C2H5)3}2] to form mainly mononuclear organocobalt complexes. Reaction of 1b with NO and the diazoalkanes di-t-butyl-diazomethane and 2-diazo-1,1′,3,3′-tetramethylcyclohexane results in the formation of the dinuclear complexes [{(η5-Cp*)CoNO}2], [{(η5-Cp*)(di-t-butyl-diazomethane)Co}2] and [{(η5-Cp*)(2-diazo-1,1′,3,3′-tetramethylcyclohexane) Co}2], respectively. In the reaction of 1b with elemental sulfur the formation of a tetranuclear Co-sulfide cluster is observed. In the majority of the reactions studied, l b looses its toluene ligand already at room temperature indicating an unusual high and hitherto unprecedented reactivity of an arene triple decker complex.