bluuebunny/crossref_metadata_2025 huggingface dataset:
A Simple Synthesis for Phenothiazin-ols and their Sulfoxides
Authors: Jain Surendra K. , Agarwal Nand Lai
Published: February 2015

A number of new hydroxyphenothiazines (2) are synthesised by the reduction of corresponding 3H-phenothiazin-3-ones with sodium dithionite and zinc dust-acetic acid. The oxidation of acetoxyphenothiazines (3) with H2O2 in acetone-ethanol provided directly substituted 2-methoxyphenothiazin-3-ol-5-oxides (5). Two series of acetylated derivatives viz. O- and O,N-acetylated of 2 were prepared.
Übergangsmetallkomplexe von Diazenen, XIV [1] Photochemische Darstellung und Reaktionen von (η1-2.3-Diazanorbornen)Fe2(η5-C5H5)2(CO)3 / Transition Metal Complexes of Diazenes, XIV [1] Photochemical Synthesis and Reactions of (η1-2.3-Diazanorbornene)Fe2(η5-C5H5)2(CO)3
Authors: Battaglia R. , Mastropasqua P. , Kisch H.
Published: February 2015

Irradiation of (η5-C5H5)2Fe2(CO)4 in the presence of 2,3-diazanorbornene affords (η1-2,3- diazanorbornene)-Fe2(η5-C5H5)2(CO)3 (1) and small amounts of (η2-2,3-diazanorbornene)Fe2-(η5-C5H5)2(CO)2 (2). 1 is converted into 2 upon heating but not upon photolysis.
Beiträge zur Chemie des Bors, CIX [1]. Neue Fünfringheterocyclen des Bors: Triazaborolidine mit Silicium, Phosphor uud Arsen als Ringglieder / Contribution to the Chemistry of Boron, CIX [1]. New Five-Membered Heterocycles of Boron: Triazaborolidines Containing Silicon, Phosphorus and Arsenic as Ring Atoms
Authors: Barlos K. , Nöth H.
Published: February 2015

1,2,4-Triaza-3-sila-5-borolidines (1) are accessible via N,N′-dilithio-N,N′-dimethyl- hydrazine and Br(CH3)B-NCH3-Si(CH3)2Br or by transsilylation of the permethyl derivative of 1. Similarly, phosphorus halides replace the (CH3)2Si group of heptamethyl- triaza-3-sila-5-borolidine (2), affording triaza-3-phospha-5-borolidines, while AsCl3 yields 3-chloro-1,2,4,5-tetramethyl-1,2,4-triaza-3-arsa-5-borolidine. Nucleophilic replacements at the P atom of 3-chloro-triaza-3-phospha-5-borolidine (9) are readily achieved. Surprisingly, the various substituents at the P atom of the new heterocyclic systems have little influence on δ11B, in contrast to δ1H. This is attributed to π- and σ-effects. It is assumed that the new ring systems are nonplanar.
Zur Chemie des 1-Aza-2-bora-3-oxacyclopentansystems / The Chemistry of the 1-Aza-2-bora-3-oxacyclopentane System
Authors: Köhn Heinz-Gerhard , Melier Anton
Published: February 2015

Derivatives of 1-aza-2-bora-3-oxacyclopentane are easily prepared by cleavage of the N-Si and O-Si bonds in disilylated ethanolamines with halogenoboranes. The B-halogeno and B-hydro compounds with NH and N-CH3 moieties are associated in the solid state, and in part also in the liquid and gas phase. In the solid phase hexahydroborazine derivatives are formed by association. Further compounds include B-N-Si-substituted rings and interlinked bicyclic systems.
Untersuchungen an quartären Pyridiniumsalzen, X [1] Eine Kondensationsreaktion von 3-Cyanpyridiniumsalzen bei Einwirkung A Condensation Reaction of 3-Cyanopyridinium Salts on Addition of Alcoxides
Authors: Gündel Wolf-H.
Published: February 2015

1-Benzyl-3-cyanopyridinium salts, in the benzyl moiety differently substituted, react in boiling alcohol with alcoxides to derivatives of hexahydro-dipyrido[l,2-a:3',2'-c]-pyrrole. At 20 °C occurs rearrangement to derivatives of 2-amino-3-pyridinecarbaldehyde.
Notizen: Zur Elektronenstruktur hochsymmetrischer Verbindungen der f-Elemente, XIV [1]. Präparation von Brom-Elpasolithen für optische Untersuchungen / The Electronic Structure of Highly Symmetrical Compounds of the f-Elements, XIV [1]. The Preparation of Bromo-Elpasolites for Optical Measurements
Authors: Amberger Hanns-Dieter
Published: February 2015

The preparation of completely clear bromoelpasolites Cs2NaLnBr6 is described. The particular suitability of the resulting products for spectroscopical measurements is demonstrated by the electronic Raman spectrum of Cs2NaPrBr6. Using the crystal field parameter set B4
0 = 232 and B6
0 = 17 cm-1 a good agreement between observed and calculated signals could be achieved.
Nitrido-und Oxochlorokomplexe des Vanadiums(V); die Kristallstruktur von AsPh4 [V0C14] Nitrido and Oxochloro Complexes of Vanadium(V); the Crystal Structure of AsPh4[VOCl4]
Authors: Beindorf Gisela , Strähle Joachim , Liebelt Wolfgang , Dehnicke Kurt
Published: February 2015

The complexes AsPh4[Cl4V = N-Cl] and AsPh4[VOCl4] are prepared by the reaction of AsPh4Cl with Cl3VNCl and VOCl3, respectively. The IR spectra indicate C4v symmetry for the complex anions with multiple VN and VO bonds and a linear arrangement for the VNCl-group. AsPh4[VOCl4] crystallizes in the tetragonal space group P4/n with two formula units in the unit cell. The crystal structure was solved by X-ray diffraction methods (R = 0,062, 1096 observed, independent reflexions). The structure consists of AsPh4+ cations and [VOCl4]- anions with symmetry C4v. The extremely short VO bond length corresponds with a VO triple; its steric requirements cause the relatively large bond angle OVCl of 103.4°.
Ein Ylidkomplex des Rutheniums mit drei-und viergliedrigen Metallocyclen / An Ylide Complex of Ruthenium with Three-and Four-Membered Metallocycles
Authors: Schmidbaur H. , Blaschke G.
Published: February 2015

A spirometallocyclic complex of ruthenium with (CH3)2P(CH2)2, (CH3)2PCH2 and two (CH3)3P ligands (formula 5) is synthesized from (CH3)2P(CH2)2Li and trans-[(CH3)3P]4RuCl2 in the molar ratio 2:1. Two equivalents of (CH3)3P are liberated and the ionic complex trans-[(CH3)3P]4Ru[CH2P(CH3)3]Cl +Cl- is formed as a by-product. The products were characterized by analytical and spectroscopic data.
Studies on Vitamin B12 and Related Compounds, 50 Synthesis of Substituted Alkylcobalamins from Vitamin B12r and Radicals Generated from Aldehydes, Alcohols and Ethers under "Oxidizing-Reducing" Conditions. A New Synthesis of Coenzyme B12 [1]
Authors: Schrauzer Gerhard N. , Hashimoto Masao , Maihub Abdussalam
Published: February 2015

Organic radicals generated by the oxidation of aldehydes, alcohols and ethers under reducing conditions are trapped by vitamin B12r to yield substituted organocobalamins. From higher n-alkyl aldehydes, acylcobalamins are formed. With acetaldehyde, a mixture of acetylcobalamin and of methylcobalamin is obtained due to the spontaneous decarbonylation of the CH3CO· radical. From saturated alcohols, w-hydroxyalkylcobalamins are produced, while w-alkoxyalkylcobalamins are formed in the corresponding reactions with radicals generated from ethers. Maximum yields of the organocobalamins are obtained if reducing conditions are maintained during the oxidation of the organic substrates. This is conveniently achieved by using V(III) salts as the reductants and the slow addition of oxidants (e.g. of O2, H2O2, Fenton reagent, or of electrochemically generated oxidizing equivalents). With 5′-deoxyadenosine, 5′-deoxyadenosylcobalamin is formed.
Semicobaltate -Alkalimetall-Träger in Kohlenwasserstoffen Darstellung, Eigenschaften und Struktur von K[Co(C2H4)(PMe3)3]2 / Semicobaltates -Alkali Metal Carriers in Hydrocarbons Synthesis, Properties, and Structure of K[Co(C2H4)(PMe3)3]2
Authors: Klein Hans-Friedrich , Groß Joachim , Bassett Jean-Marie , Schubert Ulrich
Published: February 2015

Semicobaltates (Co-1/2) containing olefin and trimethylphosphane ligands are synthe-sized from Co(olefin)(PMe3)3 and potassium metal. The X-ray crystal structure determination of the title compound shows that the unit cell contains two K atoms in equal ionic contact with the ethylene ligands of four Co(C2H4)(PMe3)3 complex units, two of which are interacting with both K atoms.

In solution the semicobaltates exist in hydrocarbon solvents under argon only, while in contrast under ethylene or nitrogen atmospheres or in donor solvents disproportionation occurs to give Co(O) and Co(-I) species. Allgemeines
Chlor-Isotopenseparation an einem wasserhaltigen Zirkondioxidaustauscher / Chlorine Isotope Separation Using an Hydrous Zirconium Dioxide Exchanger
Authors: Heumann Klaus G. , Baier Klaus , Wibmer Gerald
Published: February 2015

Hydrous zirconium dioxide is used in column experiments for separating the halide ions as well as for isotope fractionation of chlorine. The preparation of the zirconium dioxide particles is carried out by homogeneous hydrolysis of a zirconyl chloride solution using hexamethylenetetramine. The separation order of the halides is I-, Br- and Cl- in contrast to the inverse separation order using a strongly basic anion exchange resin. In chlorine isotope separation experiments an enrichment of 35Cl- is found in the first fractions, whereas the last fractions show a significant enrichment of 37C1-. This also indicates an inversion of the isotope separation compared with a strongly basic anion exchange resin. A dependence of the isotope fractionation on the concentration of the NaNO3 solution used as eluant is found. With increasing concentration the isotope fractionation decreases. Using a 0.5 M NaNO3 solution the elementary separation effect was calculated e = 6,1 · 10-4 . This is one of the highest isotope fractionations known in a chloride isotope exchange system. The results show that the electrolyte behaviour of isotopes is comparable to that of a series of homologous elements.
Über das Bis(chlorschwefel)sticktoff-Kation N(SCl)2
+/On the Bis(chlorosulfur)nitrogen Cation N(SCl)2
+
Authors: Glemser Oskar , Kindler Eckehard , Krebs Bernt , Mews Rüdiger , Schnepel Frank-Michael , Wegener Joachim
Published: February 2015

The synthesis of N(SCl)2
+ MF6
- (M = As, Sb) is reported, the structure of N(SCl)2
+ AlCL4
- is determined and some of the spectroscopic properties of the N(SCl)2
+ cation are discussed.
Reaktion von Bismuttrichlorid mit N,Nʹ-Bis(trimethylsilyl)-harnstoff und Aceton/Reaction of BiCl3 with N,Nʹ-Bis(trimethylsilyl)urea and Acetone
Authors: Georgiades A. , Schilling G. , Latscha H. P.
Published: February 2015

The reaction of BiCl3, N,Nʹ-bis(trimethylsilyl)urea and acetone yields compound 1 with the formula C22H46Cl9N8O7Bi. After treatment of 1 with acetone/dimethylformamid the spirocompound 4,4,10,10-tetramethylspiro[5,5]-1,3,7,9-tetrazaundecadion-2,8 (3) could be isolated. The structure of 3 is described and a reaction mechanismus is proposed.
Nonenzymatic Catalysis by Metal Ions and Phosphoric Acid Esters of Hydroxamic Acid Formation
Authors: Saygin Oemer , Decker Peter
Published: February 2015

Nonenzymatic catalysis by bivalent ions of Be, Mg, Ca, Zn, Mn, Ni and Co and bioorganic phosphates of the formation of hydroxamic acids from acetate or amino acids has been studied systematically. Increased yields of hydroxamate were observed at particular combinations of reactants. The most prominent increase (ca. 15-fold) was found with acetate and Ni++, and with a combination of ATP and Be++. Among others especially ribose-5-phosphate and glucose-5-phosphate enhanced yields in the presence of most metal ions. Since no release of inorganic phosphate was observed, this effect cannot be interpreted as an evidence for intermediate transhosphorylation reactions; it may also result from simple catalytic effects of metal sugar complexes.
Singlet Oxygen Production Photosensitized by Fluorescein in Reversed Micellar Solutions
Authors: Miyoshi Norio , Tomita Giiti
Published: February 2015

The quantum yield of singlet oxygen production was investigated in dodecylammonium propionate reversed micellar solutions containing 1,3-diphenylisobenzofuran and fluo-rescein as photosensitizer. The quantum yield was highly enhanced by the binding of fluorescein to reversed micelles, and increased with decreasing the solubilized water content in reversed micelles. Results obtained was discussed with the optical properties of fluorescein (absorption, fluorescence and phosphorescence) in reversed micellar solutions.
Buffer Action of Reversed Micelles
Authors: Miyoshi Norio , Tomita Giiti
Published: February 2015

The optical properties (absorption and fluorescence) of fluorescein sodium were investi-gated with changing the bulk pH value in aqueous, water-methanol mixed and dodecyl-ammonium propionate reversed micellar solutions. A strong buffer action was found in the reversed micellar solutions. The pKa values for the equilibrium between fluorescein mono-and di-anions in the ground and excited singlet states highly decreased in the reversed micellar solutions compared with those in non-micellar solutions. The micellar buffer action strongly affected the initial rate of the 1,3-diphenylisobenzofuran oxidation caused by the photosensitization of fluorescein. The buffer action was closely related to the solubilized water content.
Pyrroloquinolines, Part III [1] Synthesis of lH-Pyrrolo(2,3-b)quinolines
Authors: Murugesan M. , Ramasamy K. , Shanmugam P.
Published: February 2015

A new route to synthesis of pyrrolo(2,3-b)quinolines is described based on the use of 2-chloro-3-vinylquinolines as well as 2-chloro-3-(1ʹ,2ʹ-dibromoethyl)quinolines.
Study on Trimethylsiloxyalkanols
Authors: Kanjolia R. K. , Gupta V. D.
Published: February 2015

Trimethylsiloxyalkanols and their tributyltin(IV) derivatives have been synthesized and the nature of the species present in solution has been discussed on the basis of spectral data.
Notizen: Über zwei Bleiantimonphosphate mit Eulytinstruktur: Pb3SbIII(PO4)3 und Pb11SbV(PO4)9/On two Lead Antimony Phosphates with Eulytine Structure: Pb3SbIII(PO4)3 and Pb11SbV(PO4)9
Authors: Engel Günter , Belgardt Jutta
Published: February 2015

Two lead antimony phosphates have been prepared, which both crystallize with the cubic eulytine structure. Pb3SbIII(PO4)3 has the lattice constant a= 1037.2 pm and Pb11SbV(PO4)9 has a = 1037.5 pm. The X-ray diffraction diagrams appear nearly identical. In their chemical and thermal behaviour these compounds differ in a characteristic manner, however. The relatively large cell volume of Pb3Sb(PO4)3 is attributed to the very distinct stereochemical activity of the lone electron pair of Sb3+.
Notizen: Synthese und Struktur von Bis(dimethylgallinm)N.Nʹ-dimethyldithio-oxamid/Preparation and Structure of Bis (dimethylgallium )N ,Nʹ-dimethyldithio-oxamide
Authors: Haider Tilman , Hausen Hans-Dieter , Weidlein Johann
Published: February 2015

Monomeric Bis(dimethylgallium)N,Nʹdimethyldithiooxamide has been prepared by the reaction of Ga(CH3)3 and [HN(CH3)C(=S)-]2 in a 2:1 molar ratio. Two configurational isomers are formed and according to the 1H NMR and vibrational spectra both forms of these molecule consist of two fused five-membered rings, with an almost planar structure. The preliminary results of the X-ray structure determination are given.
Notizen: On the Role of the Electronic Bulk Properties of Semiconducting Minerals in their Interaction with Electrolytes
Authors: Kunze O. A.
Published: February 2015

The presence of small amounts of copper in galena-electrolyte systems leads to similar effects as those which can be ascribed to variations in the bulk electronic properties of semiconducting minerals. It is shown how trace amounts of copper can influence reproducibly the dissolution rate, the electrical polarizability and the rest potential of galena.
Europium(II) Heptaphosphide EuP7 [1] Europium(II)heptaphosphid EuP7 [1]
Authors: Schnering Hans Georg von , Wittmann Manfred
Published: February 2015

The novel polyphosphide EuP7 was prepared under controlled conditions by the reaction of the elements in salt melts at 750-800 K. EuP7 forms black prismatic crystals not attacked by diluted mineral acids and bases. The thermal decomposition yields EuP3 at 700 K and in further steps EuP2, Eu3P4 and EuP, respectively. According to the crystal structure as well as the electrical, optical and magnetic properties EuP7 is a semiconductor (EG = 0.9 eV; EG (vert) = 1.1 eV) with divalent europium (μ = 7.55 B.M.). The compound crystallizes in the monoclinic space group P21/n with a = 1148.8(7) pm, b = 570.0(3) pm, c = 1061.0(6) pm, and β= 106.08°(5); (X-ray diffraction data; 1479 hkl, R = 0.031). The P-atoms are connected (P-P) = 218.0-223.5 pm) to a 2-dimensional infinite polyanionic structure

with homonuclear 3-bonded and 2-bonded P-atoms in the ratio 5:2. The polyanionic network contains P6-rings (chair conformation) as well as P8-rings and P10-rings. The Eu-atoms are bonded to 9 P-atoms (1,4,4-polyhedra) with bond distances ranging from 306.6 to 326.6 pm. The Eu-atoms complete the tetrahedral environment of the P-atoms
Beiträge zur Chemie des Siliciums und Germaniums, XXXII [1]. Isomerisierung von höheren Silanen mit Aluminiumchlorid / Contributions to the Chemistry of Silicon and Germanium, XXXII [1]. Isomerization of Higher Silanes with Aluminium Chloride
Authors: Fehér Franz , Ocklenburg Franz , Skrodzki Dieter
Published: February 2015

n-Tetrasilane, n-pentasilane and n-hexasilane have been heated with aluminium chloride in different solvents. In aromatic solvents besides competitive disproportionation reactions isomerization reactions occur, whereas in non-aromatic solvents only decomposition can be observed. The conditions have been investigated, where isomerization reactions predominate and from n-tetrasilane iso-tetrasilane, from n-pentasilane iso-and neo-pentasilane as well as from n-hexasilane 2-silylpentasilane, 3-silylpentasilane, 2,3-disilyltetrasilane, and 2,2-disilyltetrasilane are formed in good yields
Tellurium in Organic Synthesis, IX [15]. Oxidation of Some Nitrogenous Compounds with TeO2
Authors: Bergman Jan , Engman Lars
Published: February 2015

Some phenylhydrazines were readily converted to diaryltellurium dichlorides in 27-40% yield when treated with TeO2 in refluxing acetic acid containing lithium chloride. It was also found that certain ketones could be regenerated from their corresponding semicarbazones, azines and hydrazones when submitted to the same reaction conditions
Totalsynthese von Somatostatin-28 (Big-Somatostatin) / Total Synthesis of Somatostatin-28 (Big Somatostatin)
Authors: Wünsch E. , Moroder L. , Gemeiner M. , Jaeger E. , Ribet A. , Pradayrol L. , Vaysse N.
Published: February 2015

The total synthesis of the octacosapeptide corresponding to the proposed primary structure of porcine somatostatin-28, a possible precursor of somatostatin, is described. The primary structure of somatostatin-28 corresponds to that of somatostatin elongated at the N-terminus by a tetradecapeptide sequence. The synthesis has been performed using the strategy of overall acid labile side chain protection based on tert-butanol and adamantol derived protecting groups in combination with the S-tert-butylthio group for the reversible blocking of the cysteine thiol functions and the Nα -2-nitrophenylsulfenyl group for the chain elongation steps. Upon assembly in sequence order of the four suitably protected fragments related to sequence 18-28, 15-17, 8-14 and 1-7, respectively, reductive cleavage of the S-tert-butylthio groups from the fully protected octacosapeptide, followed by acidolytic deprotection via exposure to trifluoroacetic acid and subsequent air oxidation led to crude somatostatin-28. Purification by gel filtration on Biogel P 6 and ion exchange chromatography on Biogel CM 2 produced the desired product in satisfactory yields and at a high degree of purity as judged from different analytical tests. The correctness of the proposed primary structure was ultimately proofed by comparative analysis of the synthetic and natural product by means of chromatographic, immunological and biological assays
AB2X2 - Verbindungen im CaAl2Si2-Typ, VII [1] Zur Struktur der Verbindungen SrZn2As2, SrCd2As2 und YbMnCuP2 / AB2X2 Compounds with the CaAl2Si2 Structure, VII [1] The Crystal Structure of SrZn2As2, SrCd2As2, and YbMnCuP2
Authors: Mewis Albrecht
Published: February 2015

The compounds SrZn2As2, SrCd2As2, and YbMnCuP2 have been prepared and their structures determined. They are isotypic and crystallize trigonally in a CaAl2Si2-type structure (space group P3̄m 1) with the lattice constants:

SrZn2As2 a = 422,3(1) pm, c = 726,8(1) pm,

SrCd2As2
a = 445,2(1) pm, c = 741,6(1) pm,

YbMnCuP2 a = 394,9(1) pm, c = 648,4(1) pm.
Darstellung und Struktur der Verbindung CaCu4P2 / Preparation and Crystal Structure of CaCu4P2
Authors: Mewis Albrecht
Published: February 2015

of the system Ca-Cu-P resulted in the discovery of CaCu4P2. The compound crystallizes in a trigonal-rhombohedral structure (hexagonal axes: a = 403.6(1) pm, c = 2227.2(2) pm; space group R3̄m) which contains structural elements of the compound CU3P.
Mineralization of CCl4 and CCl2F2 on Solid Surfaces
Authors: Gäb Siegmar , Schmitzer Johannes , Turner Walter V. , Korte Friedhelm
Published: February 2015

The mineralization of 14CCl4 and 14CCl2F2 in the dark is shown to be greatly dependent on the nature of the solid surfaces to which they are exposed, alumina being more effective than silica gel and a number of natural sands. Activation of the solids by drying or mechanically by tumbling leads to increased mineralization rates.
(MePNMe)4S3, ein Cyclotetra(λ3,λ5,λ5,λ5-phosphazan) / (MePNMe)4S3, a Cyclotetra(λ3,λ5,λ5,λ5-phosphazan)
Authors: Zeiß Werner , Schwarz Wolfgang , Hess Heinz
Published: February 2015

Octamethylcyclotetra(λ3-phosphazane) (1) reacts with three mole equivalents of sulfur, added either in excess or in deficite, to give 2, the first cyclotetra(λ3,λ5,λ5,λ5-phosphazane). Its crystal structure determination shows a completely unsymmetrical molecule, which does not undergo ring inversion in solution. Thus an ABMX spin system with remarkably different AM and BM coupling constants is observed in the 31P{1H} NMR spectrum. By means of selective {31P} decoupling, all CH3 proton signals could be assigned in the 1H NMR spectrum.
Structures of 1-Phenyl-3-methyl-pyrazolone-5 and its Benzoyl Derivatives+
Authors: Okafor Emmanuel Chukwuemeka
Published: February 2015

The structures of 1-phenyl-3-methyl-pyrazolone-5 and its benzoyl derivatives have been investigated by means of IR, UV, NMR, and mass spectral spectroscopy. 1-Phenyl - 3-methyl-pyrazolone-5 is found to exist as a zwitter ion in the solid state, in the 5-keto form in chloroform and dioxane, and in the 5-hydroxy form in pyridine. The 4-benzoyl derivative of 1-phenyl-3-methyl-pyrazolone-5 is shown to exist in two different tautomeric enol forms and not an enol form and a keto form as was formerly reported. The structures of two other benzoyl derivatives were investigated and assigned as the C-5-O-benzoyl derivative and C-4-benzoyl-C-5-O-benzoyl derivative, respectively.
Electrophilic Substitution of Aromatic Compounds by Unsaturated Sugar Derivatives
Authors: Grynkiewicz Grzegorz , Zamojski Aleksander
Published: February 2015

Hexenopyranosyl Carbocations, Pent-2-enopyranos-4-ulosyl Carbocations Glycals 1 and 2 react with methoxybenzene in the presence of SnCLj forming ^-substi-tuted C-glycosyl compounds 4 and 5 + 6 respectively. Under similar conditions 1-O-benzoyl-or methyl pent-2-enopyranos-4-uloses (7) and (8) react with electron rich aromatic compounds furnishing either C-glycosyl compounds or C-2 aryl substituted products depending on the nature of the aromatic component as well as the kind of substituent at C-1.
Darstellung und Eigenschaften von (Trifluor)acetylphosphol / Preparation and Properties of (Trifluoro)acetylphosphole
Authors: Lindner Ekkehard , Frey Gerhard
Published: February 2015

The acylphospholes

which are available from dibenzophosphole and the anhydrides [RC(O)]2O react in ether with rigorously dried molecular oxygen to the (trifluoro)acetylphosphole oxides

(2a, b), which are extremely sensitive towards nucleophiles. With stoichiometric amounts of water the P-C bond in 2a, b is cleaved hydrolytically. As a result of this hydrolysis in several reaction steps one obtains the phosphorylated alcohols

(3a, b). Particularly in solution 3b is transformed quickly into the thermodynamic more stable phosphinate

(4b). The chemical and spectroscopical pro­perties of the acylphospholes 1a, b and their derivatives are compared with the correspon­ding already known acyl(diaryl)phosphanes.
The Crystal Structures of U2Cu3 Al and UCUAl2, and their Relationship with Some Other Phases in the System U-Cu-Al
Authors: Blažina Ž. , Ban Z.
Published: February 2015

X-ray investigations of a great number of samples along the specifically chosen tie-lines in the isothermal sections of the system U-Cu-Al (800 °C) indicated the existence of two new ordered ternary phases, i.e. U2Cu3Al and UCuAl2.

The first one is hexagonal (S. G. P63/mmc, MgZn2-type), with a = 5.065 ± 0.005 Å, c = 8.307 ± 0.005 Å and c/a = 1.640. The ordered atomic arrangement of all atoms, as confirmed by trial and error method is consistent with a rather uncommon superstructure of the MgZn2-type.

UCuAl2 is tetragonal, a = 3.857 ± 0.005 A, c = 8.736 ± 0.005 A, c/a = 2.265, probable space group is I4/mmm, and represents an ordered ternary structure variant of the TiAl3 type.

The crystal structures of these two new phases were correlated, in terms of stacking sequences, with those which were identified in this system previously.
Dodecamethyl Bisimidotriphosphoramide (TRIPA), Part III [1, 2] The Crystal and Molecular Structure of TRIPA · H2O
Authors: Lapidaire Johannes C. P. M. , De Kok Anthoni J.
Published: February 2015

The crystal and molecular structure of dodecamethyl bisimidotriphosphoramide mono-hydrate (TRIPA • H2O, C12H38N7O4P3) has been determined by single crystal X-ray diffraction techniques. The compound crystallises in the monoclinic system, space group P2i/n with a = 9.236(3), b = 14.016(4), c = 17.534(5) A, β = 97.32(4)°, Z = 4. The building units are dimers of TRIPA • H2O. These units are separated by normal van der Waals distances. The two molecules in the dimer are connected by four hydrogen bridges involving two water molecules. The nitrogen atoms display a nearly planar hybridisation.
Übergangsmetall-substituierte Phosphane, Arsane und Slibane, XXIV [1] Funktionelle Arsanliganden durch Reaktion von Übergangsmetalldimethylarsinsulfiden mit Aeetylhalogenid [2] / Transition Metal Substituted Phosphanes, Arsanes and Stibanes, XXIV [1] Functional Arsane Ligands via Reaction of Transition Metal-Dimethylarsinesulfides with Acetylhalide [2]
Authors: Janta Reinhard , Malisch Wolfgang
Published: February 2015

The interaction of the transition metal dimethylarsine sulfides Cp(CO)2PMe3M-As(S)Me2 (M = Mo, W) with acetylhalides yields cationic complexes bearing the Me2AsSC(O)Me or Me2AsCl(Br) ligand, respectively. In a first step, the salt [Cp(CO)2PMe3M-AsMe2SC(O)Me]⊕X⊖ 1a-c (X = Cl, Br) is formed, which is converted by a second mole MeC(O)X into salts [Cp(CO)2PMe3M-AsMe2X]⊕X⊖ 2a-c, with (Me2CO)2S elimination. The brominated complex 2b can also be obtained by the addition of Br2 to Cp(CO)2PMe3W-AsMe2. The composition and structure of the ionic dihalogen adducts are established by NMR and IR data and by conductivity measurements.
Strukturisomere von Kupfer(I)iodid · Pyridin und ihre Lumineszenzeigenschaften. Darstellung und Kristallstruktur einer neuen Modifikation von Cul · NC5H5 / Structural Isomers of Copper(I) Iodide Pyridine and their Luminescence Properties Synthesis and Crystal Structure of a New Modification of Cul · NC5H5
Authors: Eitel Erika , Oelkrug Dieter , Hiller Wolfgang , Strähle Joachim
Published: February 2015

A new modification of CuI · py was prepared by the reaction of a saturated solution of CuI in CH3CN with a solution of pyridine in ethanol at 60 °C. It crystallizes monoclinic with four formula units in the space group P21/c. (CuI · py)∞ forms a polymeric ribbon structure. Contrary to the cubane-like tetrameric modification, (CuI · py)∞ does not show luminescence thermochromism. The luminescence properties of both modifications of Cul · py are interpreted.
Bis(η5-cyclopentacüenyl)N,N-Disiibstituted Dithiocarbamato(chloro)oxomolybdeniim(VI) Complexes
Authors: Sangari H. S. , Sodhi G. S. , Kaushik N. K. , Singh R. P.
Published: February 2015

Bis(η5-cyclopentadienyl)N,N-disubstituted dithiocarbamato(chloro)oxomolybdenum(VI) complexes of the type (C5H5)2MoO(S2CNR2)Cl and (C5H5)2MoO(S2CNRR′)Cl where R = Me, Et, i-Pr and R′ = cyclohexyl (cyhx) have been prepared by the reaction of stoichio­metric amounts of bis(η5-cyclopentadienyl)oxomolybderium(VI) dichloride with sodium dithiocarbamates in refluxing dichloromethane. Infrared spectral studies demonstrate that in these complexes, the dithiocarbamate ligands are bidentate. Hence a coordination number of 7 may be assigned to the molybdenum(VI) atom in each case. In addition to infrared studies, electronic spectra, NMR studies, magnetic susceptibility, elemental an­alyses and conductance measurements have been carried out for these complexes.
Electronic and Resonance Raman Spectra of the Linear Chain Mixed Valence Compound Pt(NH3)2(SCN)2I
Authors: Clark Robin J. H. , Kurmoo Mohamedally , Buse K. D. , Keller H. J.
Published: February 2015

The partially oxidized cis-Pt(NH3)2(SCN)2I has been studied by resonance Raman spectroscopy. A progression in the symmetric I-PtIV-I vibration (v1 = 120.1 cm-1), reaching as far as 8 v1, has been observed. The compound Pt(NH3)2(SCN)2I could be identified as a mixed valence solid with neutral, linear PtII···I-PtIV chains.
The Synthesis of Organometallic YlidesInteraction of Methylenetriphenylphosphorane with Bis(η5-cyclopentadienyl)-zirconium and -hafnium Dichlorides and the Molecular Structure of Bis(η5 -Cyclopentadienyl)chlorozirconylmethylenetriphenylphosphorane
Authors: Baldwin James C. , Keder N. L. , Strouse Charles E. , Kaska William C.
Published: February 2015

The interaction of (η5-C5H5)2MCl2 (M = Zr, Hf) with excess C̅H2-P⁺Ph3 in THF gives (η5-C5H5)2MCl(C̅H-P⁺Ph3) as yellow orange needles. Nuclear magnetic resonance spectra show hindered rotation about the P⁺-C̅ bond with ⊿G≠= 8.6 kcal/mole for M = Zr and 8.3 kcal/mole for M - Hf, respectively. The X-ray molecular structure of the zirconium complex shows a relatively short Zr-C bond length of 2.152 Å and a long P⁺-C̅ bond length of 1.716 Å.
Darstellung und Struktur der Verbindungen PrLi2P2, PrLi2As2 und NdLi2As2 / Preparation and Crystal Structure of PrLi2P2, PrLi2As2 and NdLi2As2
Authors: Fischer Herrad-Odilia , Schuster Hans-Uwe
Published: February 2015

Three ternary compounds PrLi2P2, PrLi2As2 and NdLi2As2 have been prepared and investigated by X-ray methods. They are isotypic and crystallize trigonally in the CaAl2Si2-structure (Space group P3̅m1-D3d
3) with the follow-ing cell parameters:

PrLi2P2: a = 419.6 pm, c = 682.1 pm;

PrLi2As2: a = 429.9 pm, c = 696.0 pm;

NdLi2As2: a = 428.7 pm, c = 692.2 pm.
Kationische Rhenium-pentacarbonyl- Komplexe mit Sauerstoff-σ-Liganden / Cationic Rhenium-pentacarbonyl Complexes with Oxygen-σ Ligands
Authors: Oltmanns Melle , Mews Rüdiger
Published: February 2015

From [Re(CO)5SO2]+AsF6
- or Re(CO)5FAsF5 and oxygen-σ-donors D (D = H2O, CH3OH, (CH3)2CO) the complexes [Re(CO)5D]+AsF6
- are formed in quantitative yield. The spectroscopic properties of the cations are reported.
Darstellung von (Trimethylsilylmetliyl)gallium-Verbindungen / Preparation of (Trimethylsilylmethyl)gallium Compounds
Authors: Fuhrmann Klaus-Dieter , Huber Friedo
Published: February 2015

(Me3SiCH2)3Ga, a monomer in benzene solution and a rather weak Lewis acid, was prepared from GaCl3 and Me3SiCH2MgCl in Et2O (Me = CH3, Et = C2H5). Et2GaCH2I, obtained from Et2GaI and CH2N2, reacts with Me3SiMgCl in Et2O to give a solution of Et2GaCH2SiMe3. This compound and PPh3 form the more stable complex Et2GaCH2SiMe3 · PPh3 (Ph = C6H5), which can be isolated.
Dynamisches Verhalten, Konformation und Bindungsverhältnisse von Enaminosulfoniumsalzen / Dynamic Behaviour, Conformation and Bonding of Enaminosulfonium Salts
Authors: Firl Joachim , Braun Heinz , Amann Anton , Barnert Robert
Published: February 2015

The rotational barriers about the C-N single bond of the enaminosulfonium salts 1-6 are measured. Their magnitudes are related to the π-donor strength of the NR2 group. For the unsymmetrically substituted compounds 7-12 the rotational equilibria are determined. In the case of the monoalkyl compounds 7-10 the more crowded s-cis-rotamers turn out to be the more stable conformations. Furthermore, the 13C chemical shifts of the sulfonium salts 1-16 are reported. The shift differences δ(s-cis-s-trans) for the α-carbons of the N-alkyl groups seem to depend on the dihedral angle between the vinyl group and the C-H(α-c) bonds. Moreover, the spectra reveal that enaminosulfonium salts posses a high degree of ylide character.
Salts of Ferricinium Cation and its Homologues: NMR Investigation, II EPR and NMR Spectra of sym-Polymethyl Substituted Ferricinium Cations
Authors: Materikova R. B. , Babin V. N. , Solodovnikov S. P. , Lyatifov I. R. , Petrovsky P. V. , Fedin E. I.
Published: February 2015

The EPR, 1H and 13C NMR spectra of methylferricinium hexafluorophosphates, [(MenCp)2Fe]PF6, n = 0-5, have been recorded. HFS constants have been estimated for all the ligand atoms. The general pattern of the spin density distribution is shown to depend on the superposition of the various mechanisms of spin delocalization. For the majority of the cations the determining factors has been found to be represented by spin polarization over the π-skeleton.
Untersuchungen an quartären Pyridinium-Salzen, XIII [1] Reaktion von Carbonsäureamiden mit Pseudobasen der Pyridinreihe / Investigations of Quaternary Pyridinium Salts, XIII [1] Reaction of Carboxamides with Pseudobases from Pyridine Derivatives
Authors: Gündel Wolf-H.
Published: February 2015

Pyridinium salts react in aqueous solution to pseudobases, which give on addition of carboxamides N-(1,4-Dihydro-4-pyridyl)-carboxamides.
The Chemical Evolution of a Nitrogenase Model, XIX Simulation of the Enzymatic Reduction of Cyclopropene
Authors: Schrauzer Gerhard N. , Hughes Laura A. , Palmer Miles R. , Strampach Norman , Grate Jay W.
Published: February 2015

The nonenzymatic reduction of cyclopropene in molybdothiol-and related model systems of nitrogenase yields cyclopropane and propylene in a pH-dependent fashion: In alkaline media, cyclopropane is formed exclusively. In acidic solutions, cyclopropane and propylene are produced. Cyclopropene is thus identified as a pH sensitive chemical probe of nitrogenase. Since substantial amounts of propylene are formed in the enzymatic reduction of cyclopropene, it follows that the active site in functioning nitrogenase is in a locally acidic environment. The protons required to sustain the acidic pH are presumably generated by ATP hydrolysis; addition of substrate amounts of ATP to nonenzymatic cyclopropene reducing systems also stimulates propylene-and cyclopropane production. The stereochemical course of cyclopropene reduction to cyclopropane is exclusively cis, both under enzymatic and nonenzymatic conditions. The formation of propylene from cyclopropene is not stereoselective and mechanistically consistent with acid catalyzed ring opening prior to reduction.
1,2-Dimethoxy-4-isopropoxy-5-vinylbenzene, an Insect anti-Juvenile Hormone Lacking the Chromene Ring
Authors: Matolcsy G. , Darwish Y. M. , Bélai I. , Varjas L. , Farag A. I.
Published: February 2015

The chromene derivative precocene II (1) induces precocious metamorphosis and sterility on some insects, while β-asarone (2), which does not contain a chromene ring, reveales sterilant action without causing developmental disturbances. Based on the common structural features of these two substances, some of their analogues containing their structural elements have been prepared and tested on the cotton bug, Dysdercus cingulatus to investigate structural requirements of activity. The title compound 3 lacking the chromene ring induced symptoms similar to those of precocene II, indicating that the chromene ring structure is not necessary for this action.
Alkaloide in Tabernaemontana-Arten, XIII [1] Ibophyllidin und Ibophyllidin-Nb-oxid, Alkaloide in Tabernaemontana flavicans / Alkaloids in Tabernaemontana-Species, XIII [1] Ibophyllidine and Ibophyllidine-Nb-oxide, Alkaloids in Tabernaemontana flavicans
Authors: Achenbach Hans , Raffelsberger Bernd
Published: February 2015

From the basic extract of Tabernaemontana flavicans we isolated the alkaloids 1 and 2 and deduced their structures. Both compounds belong to the relatively rare group of 21-norpandolane type alkaloids.
Solid Phase Synthesis of Thymopoietin-(32-36) Using Adpoc Amino Acids and its Biological Activity +
Authors: Rampold Georg , Lundanes Elsa , Folkers Karl , Voelter Wolfgang , Kalbacher Hubert , Bliznakov Emile
Published: February 2015

An exemplary peptide has been synthesized for the first time by an automated solid-phase instrumentation which utilized the new Adpoc (1 -(1-adamantyl) -1 -methylethoxycarbonyl-) group for protection of the a-amino groups of the amino acids. The pentapeptide, thymo-poietin-(32-36) was synthesized, and shown to be pure by criteria including HPLC. Using a Cytoxan (cyclophosphamide) model system for suppression of a primary, hemolytic, humoral, antibody level, thymopoietin-(32-36) showed low activity, and reversed the suppressing effect of Cytoxan. This biological activity apparently is the result of cummulative effect.
Optisch aktive Übergangsmetall-Komplexe, LXX [1]. Darstellung der optisch aktiven Diastereomeren C5H5Fe(CO)- (CH2OCH3)P(C6H5)2N(CH3)R* mit chiralen Fe-Atomen / Optically Active Transition Metal Complexes, LXX [1]. Preparation of the Optically Active Diastereoisomers C5H5Fe(O)- (CH2OCH3)P(C6H5)2N(CH3)R* with Chiral Fe Atoms
Authors: Brunner Henri , Leblanc Jean-Claude
Published: February 2015

The two diastereoisomers C5H5Fe(CO)(CH2OCH3)P(C6H5)2N(CH3)R* (Ba, b), with R* = (S)·CH(CH3)(C6H5), differing only in the Fe configuration, have been obtained by photochemical reaction of C5H5Fe(CO)2CH2OCH3 with (S)-(+)-P(C6H5)2N(CH3)R*. The optically pure isomer 3 a can be isolated by chromatography at low temperature; its chiroptical properties are discussed.
Mesylhydroxylamine, IV [1] Silylierte N-Mesylhydroxylamine / Mesylhydroxylamines, IV [1] Silylated N-Mesylhydroxylamines
Authors: Pohlmann Gerd , Brink Klaus , Bliefert Claus
Published: February 2015

The preparation and some properties of the two silylated N-Mesylhydroxylamines, CH3SO2N(H)OSi(CH3)3 and CH3SO2N[Si(CH3)3]OSi(CH3)3, are reported.
Isolation of a New Natural Quinone, 2-Hydroxy-6-methoxy-3,5-dimethyl- 1,4-benzoquinone, from the Potato Culture Solution of Phoma wasabiae Yokogi
Authors: Soga Osamu , Iwamoto Hidetoshi
Published: February 2015

2-Hydroxy-6-methoxy-3,5-dimethyl -1,4- benzoquinone was found in the blackish potato culture solution of Phoma wasabiae.
Chemie polyfunktioneller Liganden, 60 [1]. Über Käfigverbindungen mit den Heteroelementen Arsen und Selen / Chemistry of Polyfunctional Ligands, 60 [1]. On Cage Compounds with the Heteroelements Arsenic and Selenium
Authors: Eilermann Jochen , Lietz Martin
Published: February 2015

The reaction of 1,1,1-tris(diiodoarsinomethyl)ethane, CH3C(CH2Asl2)3 (1) with NaAs(C6H5)2 in the molar ratio of 1:3 gives 4-methyl-1,2,6-triarsa-tricyclo[2,2,1,02,6]-heptane, CH3C(CH2As)3 (2). The previously synthesized CH3C(CH2AsS)3 (4) can be desulphurated with triphenylphosphine to yield also 2. The reaction of 1 with NaSeH gives the new cage compound 6-methyl-1,3,4-triarsa-2,8-diselena-tricyclo[3,3,1,03 ,4]-nonane, CH3C(CH2As)3Se2 (5).
Zur Kenntnis von Ca4Sb2O / Preparation and Crystal Structure of Ca4Sb2O
Authors: Limartha Hadi , Eisenmann Brigitte , Schäfer Herbert , Graf Hans A.
Published: February 2015

The formerly described compound Ca2Sb is to be corrected to Ca4Sb2O as shown by X-ray diffractometer data of single crystals and neutron diffraction diagramms of powders. The compound crystallizes in the K2NiF4 structure type.
Triazido-trichloro-cyclotriphosphazen (NPClN3)3 und ein neuer Syntheseweg für [Cl3PNPCl3]Cl / Triazido-trichloro-cyclotriphosphazene (NPClN3)3 and a New Synthesis for [Cl3PNPCl3]Cl
Authors: Müller Ulrich , Schmock Fritjof
Published: February 2015

The reaction of PCl3 with ClN3 at -78 °C probably yields the extremely explosive PCl4N3; at higher temperatures (-10, 20 °C) [Cl3PNPCl3]Cl is formed. From PPh4[I(N3)2] and PCl3 the cyclophosphazene (NPClN3)3 was obtained, probably via the intermediate PCl(N3)2- (NPClN3)3 consists of a mixture of the syn and anti isomers and was characterized by its 31P NMR, IR and Raman spectra.
29Si-Kernresonanzmessungen an Polysilanen. 2. Isotetrasilane / 29Si NMR Measurements on Polysilanes. 2. Isotetrasilanes
Authors: Marsmann H. C. , Raml W. , Hengge E.
Published: February 2015

Isotetrasilanes with the general formula XSi(SiY3)3 (X = F, Cl, Br, I, CH3, OCH3; Y = CH3, OCH3, Cl) were studied by 29Si and 13C NMR. One-bond coupling constants between the silicon nuclei as well as between carbon and silicon were studied. It was found, that the magnitudes depend not only on the electronegativity of X and Y, but also on the steric effect of the substituent X.
Acetylaceton als Dien-Diolat-Ligand in 6-Methyl-4-methylen-2-phenyl-4H-1.3.2-dioxa-arsorin- Übergangsmetallkomplexen / Acetylacetone as a Diene Diol Ligand in 6-Methyl-4-methylen-2-phenyl-4H-1,3,2-dioxa-arsorine Transition Metal Complexes
Authors: Seyerl Joachim von , Huttner Gottfried , Krüger Karl
Published: February 2015

Reaction of dichlorophenylarsane complexes with acetylacetone gives 1,3,2-dioxa arsorine systems, in which both chlorine functions are substituted by the oxygen atoms of one acetylacetone moiety bonded in its diene diol form. Properties and spectra of (CO)5CrAsPh(C5H6O2) and η5-C5H5(CO)2MnAsPh(C5H6O2) are described; the structure of the (CO)5Cr complex was established by an X-ray analysis.
Steady State Radiolysis of Aqueous Aerated Solutions of 5,6-Dihydrothymine. Identification of the Major Degradation Products
Authors: Cadet J.
Published: February 2015

The major radiation-induced degradation products of 5,6-dihydrothymine (1) in aqueous solutions saturated either with O2 or N2O/O2 (75/25 v/v) were identified as thymine (10), the trans-and cis-isomers of 6-hydroperoxy-5,6-dihydrothymine (5, 7), 5-hydroperoxy-5,6-dihydrothymine (9), and their corresponding hydroxy derivatives (4, 6, 8). The formation of these compounds is explained in terms of initial H-abstraction from the C(5) and C(6) carbons which gives rise respectively to the transient 5-yl and 6-yl radicals. Thymine hydroxy-hydroperoxides (11-14) and their decomposition products (17-20), which are derived from hydroxyl radical attack at the 5,6-ethylenic bond of thymine (10), were also characterized.
Darstellung und Kristallstruktur von SbCl3I2 ·1.4-Dithian/Preparation and Crystal Structure of SbCl3 · I2 · 1,4-Dithiane
Authors: Kiel Gertrud
Published: February 2015

The darkred compound SbCl3 · I2 · S2C4H8 has been prepared and its crystal structure determined. This new compound crystallizes in the monoclinic system, space group P21, with a = 849.2 pm, b = 904.2 pm, c = 923.6 pm and β = 106.1° at a temperature of 113 K, and with a = 858.8(2) pm, b = 914.7(3) pm, c = 934.0(4) pm and β = 106.62(3)° at a temperature of 293 K, respectively. The structure is built up from chains (SC2H4S···I-I-ClSbCl2)∞ with a ψ-trigonal bipyramid around Sb.
New Furanoid Diterpenes from Teucrium scordium L.
Authors: Papanov Georgi Y . , Malakov Peter Y .
Published: February 2015

Two new furanoid diterpenes of clerodane type, 6-ketoteuscordin (1) and 6α-hydroxy-teuscordin (2) have been isolated from Teucrium scordium var. scordium, Lamiaceae. Their structures and stereochemistry have been determined.
Zur Diastereoisomerie natürlicher und synthetischer α-Bisabolole/On the Diastereoisomerism of Natural and Synthetic α-Bisabolols
Authors: Flaskamp Elmar , Nonnenmacher Gerhard , Isaac Otto
Published: February 2015

The stereochemistry of α-bisabolol is discussed. The chiralities of the different α-bisabolols from Myoporum crassifolium, Populus balsamifera and Vanillosmopsis erythropappa are deduced from the absolute configuration of natural bisabolol from chamomile, which has to be considered as being (1′S,2S)-configurated according to most recent investigations.

Based on this assumption, (1′S, 2R)-configuration has to be ascribed to (-)-α-bisabolol from Myoporum crassifolium, whereas (1′R,2R)-resp. (1′S,2S)-structure is present in (+)-α-bisabolol from Populus balsamifera and (-)-α-bisabolol from Vanillosmopsis erythropappa being therefore enantiomeric to the latter. Consequently, the (-)-α-bisabolols from Matricaria chamomilla and Vanillosmopsis erythropappa turn out to be identical in all respects.

Synthetic α-bisabolols, however, featuring approximately equal amounts of all the four possible stereoisomers, differ not only optically but also in their stereochemical uniformity from natural α-bisabolols.

By means of NMR spectrometric methods the identity of the native active agent can be established in chamomile specialities; as a consequence possible admixtures of synthetic racemates of α-bisabolol thus can be identified and quantified.
Studies on Ferrocene Derivatives(VII)./Synthesis of Some New Ferrocenyl Dibromides, Benzofuranes and Indoles
Authors: El-Khawaga A. M. , Hassan K. M. , Khalaf A. A.
Published: February 2015

A series of ferrocenyl chalcones (1-7) have been prepared by the interaction of acetylferrocene with aromatic aldehydes. Reaction of these ferrocenyl chalcones with hydrazines gave ferrocenyl pyrazolines (8-21). Also, the reaction of chalcones with bromine yielded the corresponding dibromides (22-25). Fusion of dibromides (22-25) with 2-naphthol and 1-naphthylamine gave the corresponding substituted ferrocenylbenzofuranes (26-29) and ferrocenyl endoles (30-33) respectively.
Notizen: Rhomboedrisch kristallisierende Zink-hexacyanometallate(III) Zn3[M(CN)6]2/ Rhombohedrally Crystallizing Zinc Hexacyanometalates(III) Zn3[M(CN)6]2
Authors: Siebert Hans , Jentsch Walther
Published: February 2015

The preparation of a non-cubic modification of water-free hexacyanometalates(III) Zn3[M(CN)6]2 (M = Cr, Fe, Co) is described. The X-ray powder diagrams of these compounds have been indexed rhombohedrally, space group D6
3d-R3̄c, Z = 2.
Darstellung symmetrisch bisaminierter Carbodiphosphorane R2NPh2P=C=PPh2NR2 [1] / Synthesis of Symmetrical Diaminocarbodiphosphoranes R2NPh2P=C=PPh2NR2 [1]
Authors: Appel Rolf , Waid Karl
Published: February 2015

The hitherto unknown symmetrical diamino carbodiphosphoranes

R2NPh2P = C = PPh2NR2 (5 a-d (R = CH3, Et, nPr, nBu) are obtained in good yield by NaH dehydrohalogenation of the corresponding aminophosphonium salts

3 a-d can be prepared by aminolysis of C(PPh2Cl)2 (1) or, more conveniently, directly in the three component reaction ditertiary phosphine/amine/CCl4 (31P{1H} and 13C{1H} NMR).
Die Kristallstruktur von Methyltriphenylphosphoniumhexachlorotitanat [MePh3P]2TiCl6 / The Crystal Structure of Methyltriphenylphosphonium Hexachlorotitanate
Authors: Hey Evamarie , Müller Ulrich
Published: February 2015

The crystal structure of [MePh3P]2TiCl6 was determined from X-ray diffraction data and refined to a residual index of R = 0.065. It crystallizes in the space group P2i/n with two formula units per unit cell; the cell dimensions are a - 921, b = 1314, c = 1648 pm and y - 100.87°. The TiCl6
2- ion occupies an inversion center and has the shape of a slightly distorted octahedron with Ti-Cl distances between 233 and 235 pm.
Synthese und Struktur von 1.2.3-Thiadiazol- und 1.2.3-Selenadiazol-Pentaearbonyl-Komplexen der Elemente Chrom und Wolfram / Synthesis and Structure of 1,2,3-Thiadiazol- and 1,2,3-Selenadiazol-Pentacarbonyl-Complexes of the Elements Chromium and Tungsten
Authors: Bätzel Volker , Boese Roland
Published: February 2015

From the reactions of (THF)M(CO)5 (M = Cr, W) with 4-phenyl-1,2,3-thiadiazol, 4-methyl-5-carboxylic acid-1,2,3-thiadiazol, 4-methyl-5-carboxylic acid ethyl ester-1,2,3-thiadiazol and 4-methyl-1,2,3-selenadiazol, pentacarbonyl-complexes are obtained as air stable compounds. IR spectra of products of similar reactions with M = Mo provide some evidence of the formation of analogous complexes. The thiadiazol complexes are also accessible directly, by photochemical displacement of carbonmonoxid in THF from the parent carbonyl. The X-ray structures of pentacarbonyl-(4-phenyl-1,2,3-thiadiazol)-tungsten and pentacarbonyl-(4-methyl-1,2,3-selenadiazol)-chromium show the coordina-tion of the ligand to the pentacarbonyl-metal-fragment via the nitrogen in position 2.