Published by De Gruyter

Volume 38 Issue 7

Issue of Zeitschrift für Naturforschung B

Contents
Journal Overview

Open Access June 2, 2014

N-Methylcarbamoylphosphate, I. Synthese / N-Methylcarbamoyl Phosphates, I. Synthesis

Fritz Seel, Norbert Klein

Page range: 797-803

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Abstract

Solutions of mono-and bis-N-methylcarbamoyl phosphates in non-aqueous solvents [e.g. acetonitrile, dimethyl formamide, chloroform) and, surprisingly, even in water are readily obtained by the reaction of methyl isocyanate with the solution of an appropriate mono-or dihydrogenphosphate. The course of the reactions and the limited stability of N-methylcarbamoyl phosphate ions in solutions can be monitored through 31 P NMR measurements. Various types of compounds, including a coordination compound of cobalt could be isolated in crystalline form: [Et 3 NH]HX, KHX, NH 4 HX, Na 2 X · H 2 O, MgX · 4 H 2 O, CaX · H20, SrX · 2 H 2 O, BaX · H 2 O, ZnX · 5 H 2 O, CdX · 2 H 2 O, [(NH 3 ) 5 CoX]ClO 4 , [Et 3 NH]Y, AgY · MeCN, X = MeNHC(O)OPO 3 , Y = [MeNHC(O)O] 2 PO 2 .

Open Access June 2, 2014

Bildung von Amidophosphaten und Amidophosphorsäure aus N-Methylcarbamoylphosphaten / Formation of Amidophosphates and Amidophosphoric Acid from N-Methylcarbamoyl Phosphates

Fritz Seel, N. Klein

Page range: 804-807

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Abstract

The synthesis of various amidophosphates can be readily accomplished in aqueous solutions by the reaction of amines with solutions of sodium, potassium or ammonium N-methylcarbamoyl phosphate, prepared by the reaction of methylisocyanate with the corresponding hydrogen phosphates. Procedures for the synthesis of NH 4 [O 3 PNH 3 ] and Ca[O 3 PNH 2 CH 3 ] 2 · 4 H 2 O are described in detail.

Open Access June 2, 2014

Synthese und Struktur von N₂S₃Cl+SbCI₆ - / Synthesis and Structure of N₂S₃Cl+ SbCl₆-

Wilhelm Isenberg, Nayla K. Homsy, Jens Anhaus, Herbert W. Roesky, George M. Sheldrick

Page range: 808-810

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Abstract

N 2 S 3 Cl+ SbCl 6 - was prepared by chlorination of N 4 S 4 · SbCls 5 with elemental chlorine. The crystals are monoclinic, P2 1 /c, with a = 1492.4(4), b = 1233.6(2), c = 1437.5(4) pm, β = 91.40(2)°, and R = 0.059 for 3663 observed reflections. There are two independent cations and anions in the asymmetric symmetric unit. The appreciable interionic interaction results in a high density of ρ = 2.642 g · cm -3 (calcd).

Open Access June 2, 2014

Bindungsverhältnisse und magnetische Eigenschaften ternärer Arsenide ET₂As₂ / Bonding and Magnetic Properties in Ternary Arsenides ET₂As₂

Martin Pfisterer, Günter Nagorsen

Page range: 811-814

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Abstract

The interatomic distances of ternary arsenides ET 2 As 2 with ThCr 2 Si 2 -structure were determined by X-ray powder methods (E = Ca, Sr, Ba; T = Cr, Fe, Co, Ni, Cu). The phases were found to behave according to the Zintl-Klemm-Busmann concept. Magnetic susceptibilities were measured.

Open Access June 2, 2014

³¹P−₁₅N Coupling Constants and ¹⁵N/¹⁴N Isotope Effects on ³¹P NMR Chemical Shifts of 2-Phenylamino-2-oxo(-thioxo, -selenoxo)- 4-methyl-1,3,2-dioxaphosphorinanes and Related Compounds

Willy Gombler, Ryszard W. Kinas, Wojciech J. Stec

Page range: 815-818

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Abstract

The strong influence of a chalcogen atom (O, S, Se) attached to phosphorus on the spin-spin coupling constant 1 J(P- 15 N) in the family of diastereoisomeric 2-| 15 N] -phenyl-amino-2X(X = O, S, Se)-4-methyl-l,3,2-dioxaphosphorinanes is demonstrated. The 15 N/ 14 N isotope effect on the nuclear shielding of phosphorus-31 is larger for the shorter equatorial than for the longer axial P-N bonds.

Open Access June 2, 2014

Thermoanalytische, IR-spektroskopische und quantenchemische Untersuchungen an Kristallmodifikationen des Trichlorphons / Thermo-analytical, IR-spectroscopical and Quantum-chemical Investigations on Crystal Modifications of Trichlorphone

Hans Sohr, Günter Hanschmann, Hermann Utschik

Page range: 819-824

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Abstract

Several modifications of trichlorphone can be prepared by recrystallizing the raw substance from various solvents under special conditions. One of these modifications is obviously an optical isomer. The different thermo-analytical behavior of the modifications is probably due to the relative content of distinct dimer species. This interpretation is supported by quantum-chemical calculations and by analysis of infrared spectra.

Open Access June 2, 2014

Coordinative Interactions in Chelated Complexes of Silicon, Part III Crystal and Molecular Structure of 1-Trichlorosilyl-1,2,3,4-tetrahydro-1,10-phenanthroline

Gerhard Klebe, Jan W. Bats, Karl Hensen

Page range: 825-829

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Abstract

The crystal structure of C 12 H 11 N 2 SiCl 3 (monoclinic, P2 1 /m, Z = 2, with a: 9.284(4), b: 7.226(2), c: 10.832(5) Å, β = 115.14(3)°) was refined to R(F) =0.035 from 1228 independent reflections. A trigonal bipyramidal, pentacoordinate silicon is observed. The chelated complex shows two different Si−N bonds, a coordinative bond (1.984(2) Å) between Si and N on the axial position and a Si−N single bond (1.737(3) A, equatorial plane), introduced by chemical reaction. The coordinative bond is 14.2% longer than the Si−N single bond. The lengthening of the coordinative bond in the present case is compared with distances in other extracoordinated silicon compounds.

Open Access June 2, 2014

Interaction between Acetyltetralone and Cu(II) Ions: X-Ray Diffraction of the Ligand and Single Crystal ESR Study of the Complex

Page range: 830-834

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Abstract

Single crystals of acetyltetralone grown from a solution containing a small amount of Cu(II) ions are studied by ESR. The corresponding g, 63 Cu magnetic and quadrupolar hyperfine tensors are obtained and are consistent with the trapping of a square planar copper(II) complex. X-ray diffraction shows that pure acetyltetralone crystallizes in the orthorhombic space group Pbca (a - 8.893 Å, b = 20.301 Å, c = 10.715 Å). Comparison of the ESR eigenvectors with the bond directions obtained from this crystal structure study shows that the Cu(II) complex experiences some constraint from the crystal matrix. The present complex is a model for one of the complexation sites of tetracyclines.

Open Access June 2, 2014

Aktivierung von CO₂ an Übergangsmetallzentren: Struktur und Reaktivität eines C-C-Kopplungsproduktes von CO₂ und 2.3-Dimethylbutadien am elektronenreichen Nickel(O) / Activation of CO₂ at Transition Metal Centers: Structure and Reactivity of a C-C-Coupling Product of CO₂ and 2,3-Dimethylbutadiene at Electron-Rich Nickel(O)

Dirk Walther, Eckhard Dinjus, Joachim Sieler, Nguyen Ngoc Thanh, Wolfgang Schade, Ivan Leban

Page range: 835-840

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Abstract

Carbon dioxide reacts with 2,3-dimethylbutadiene and bis-cyclooctadiene(1,5)-nickel(O) in the presence of N,N′-tetramethyl-ethylendiamine (tmeda) to form [(3,4,5-η 3 )-3,4-dimethyl-3-pentenylato](N,N′-tetramethyl-ethylendiamine)-nickel(II) as the product of the oxidative coupling of CO 2 and the diene. The deep red complex crystallizes in the rhombic space group Pbca. The structure was determined by an X-ray analysis. The monodendate carboxylate group, the π-allyl system and a N-atom of tmeda form a planar coordination sphere around the central atom. The distance between Ni and the second N-atom of tmeda is very long (2.314 Å). Reaction of the complex with R−X (R: H, CH 3 ) yield 3-unsaturated carboxylic acids; tmeda can be substituted by 2,2′-bipyridine.

Open Access June 2, 2014

Photochemische Reaktionen von Übergangsmetall-Olefin-Komplexen, VII [1] Die Reaktion von Triearbonyl-η⁶-cyclooctatetraen-chrom(0) mit 6-mono-und 6.6-disubstituierten Fulvenen / Photochemical Reactions of Transition Metal Olefin Complexes, VII [1] The Reactions of Tricarbonyl-η⁶-cyclooctatetraene-chromium(0) with 6-Mono-and 6,6-Disubstituted Fulvenes

Cornelius G. Kreiter, Hans Kurz

Page range: 841-848

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Abstract

Tricarbonyl-η 6 -cyclooctatetraene-chromium(0) (1) reacts photochemically with 6-mono- and 6,6-disubstituted fulvenes (2-7) in a substitution-oxidative rearrangement-reaction to dicarbonyl-η-1′-3':1″-5″-(cycloocta-2′,4′,6′-trien-1′,8′-ylene-cyclopentadienylidene-methane)chromium complexes (8−13). Tricarbonyl-η-6,6-dimethylfulvene-chromium(0) (16) reacts with cyclooctatetraene, bicyclo[6,1,0]nona-2,4,6-triene and anti-9-methoxybicyclo-[6,1,0]nona-2,4,6-triene in a similar manner and forms 8 and 2-bicyclo[6,1,0]nona-4′,6′-dien-2′,3′-ylene-2-cyclopentadienylidene-propane complexes (19, 20). In addition to 13 6-dimethylaminofulvene (7) yields with 1 dicarbonyl-η-1′,6′,7′: 1 ″ -5 ″ -(2-cyclohepta-2′,4′,6′-trien-7′-ylidene-1 -cyclopentadienylidene-1-dimethylamino-ethane)-chromium (14) which involves an unexpected contraction of the eight-membered ring. The constitutions of 8−15 and 19−20 were determined by IR and NMR spectroscopy. In Cr(CO) 2 [C(C 6 H 5 ) 2 (C 5 H 4 )(C 8 H 8 )] (9) one of the phenyl groups shows hindered rotation around its two fold axis.

Open Access June 2, 2014

Peroxofluorokomplexe der Übergangsmetalle, V [1-3] Kristallstruktur von K₂Ti(O₂)F₄ · H₂O (orange) mit einem Di(μ-fluoro)diperoxo-hexafluorodititanat(IV)-Anion / Transition Metal Peroxofluoro Complexes, V [1-3] Crystal Structure of K₂Ti(O₂)F₄ · H₂O (orange) with a Di(μ-fluoro)diperoxo-hexafluorodititanate(IV) Anion

Roland Schmidt, Wolfgang Hiller, Gerhardt Pausewang

Page range: 849-851

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Abstract

Orange crystals of K 2 Ti(O 2 )F 4 · H 2 O have been obtained from aqueous solution. The crystal structure (space group P2 1 /n, a = 604.3(3), b = 1424.6(4), c = 761.0(2) pm, β = 103.98°, Z = 4, dc = 2.63 gcm -3 , d m = 2.62 gcm -3 , R = 0.051 for 2257 independent reflections) shows isolated di(μ-fluoro)-bridged [Ti 2 (O 2 ) 2 F 8 ] 4- anions, which are interconnected by hydrogen bonded H 2 O forming infinite chains.

Open Access June 2, 2014

Optisch aktive Übergangsmetall-Komplexe, 84 [1] Substituenten-Effekte in Diastereomerengleichgewichten von quadratisch-pyramidalen Mo-Komplexen / Optically Active Transition Metal Complexes, 84 [1] Substituent Effects in Diastereomer Equilibria of Square-Pyramidal Mo Complexes

Henri Brunner, Beate Schönhammer

Page range: 852-857

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Abstract

Amidinato complexes with substituents R at the cyclopentadienyl and R′ in the p-position of the phenyl at the asymmetric C atom were synthesized and characterized. The diastereomers differing in their 1 H NMR spectra were partly separated by fractional crystallization. After equilibration with respect to the labile Mo configuration the diastereomer ratio, a measure for the asymmetric induction from the chiral ligand on the formation of the two Mo configurations at equilibrium, was determined by 1 H NMR integration. The diastereomer ratio decreases for substituents R′ = F and R = CH 3 , and increases for R' = OCH 3 , compared to the unsubstituted compound.

Open Access June 2, 2014

Quantum Chemical Interpretation of the Photoinitiated Autoxidation of Sulphite Catalysed by Ferric Ions

A. M. El-Wakil, M. S. Soliman, A. B. Farag

Page range: 858-860

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Abstract

Autoxidation of sulphite is the first well known chain reaction proceeding through free radicals in solutions. Dark and photochemical autoxidation of sulphite were stated to take place by the same mechanism except in the initial steps. It was found that the formation of sulphite radicals in photoinitiated autoxidation of sulphite which is a metal catalysed reaction as well as the classical thermal reaction is due to the absorption of photons by ferrisulphite complexes rather than sulphite itself. Confirmation of this finding was achieved spectrophotometrically as well as by the fact that such complexes are specified by very high stability constants. The present work is a further evidence for the presence of such complexes and to cover the gap present before in the literature data. Quantum mechanical calculations using the extended Hückel molecular orbital method has proved that the range of absorption by sulphite lies in a region at which sulphite alone does absorb at all, and the absorption process is thus due to the formation of ferrisulphite complexes.

Open Access June 2, 2014

Reaktionen des Hexaphenylcarbodiphosphorans, IV [1] Reaktionen des Hexaphenylcarbodiphosphorans mit Halogenverbindungen. Diphosphaallylkationen / Reactions of Hexaphenylcarbodiphosphorane, IV [1] Reactions of Hexaphenylcarbodiphosphorane with Halogen Compounds. Diphosphaallyl Cations

Hans Jürgen Bestmann, Helmut Oechsner

Page range: 861-865

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Abstract

Hexaphenylcarbodiphosphorane (1) undergoes nucleophilic displacement reaction with halogen compounds 3 with formation of compounds 5 which can be regarded as salts of the diphosphaallylcation. 1 reacts with bromoacetic ester 11 as base, with proton abstraction and formation of a carbanion 12 which gives rise to formation of (E)-cyclopropan-tricarboxylicacid ester (13). In an analogous way, 1 attacks isothiocyanatoaceticacid ester (14) with formation of an ionpair 15 which undergoes a cycloaddition with a second molecule 14 forming 16, which can be converted into the mercaptothiazol derivative 17 by treatment with HCl.

Open Access June 2, 2014

Zur Synthese von substituierten Phenazinen aus Benzofurazanoxid und Hydrochinonen [1] / Synthesis of Substituted Phenazines from Benzofurazanoxid and Hydroquinones [1]

A. Römer, M. Sammet

Page range: 866-872

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Abstract

The sterical course of the formation of substituted phenazines from benzofurazanoxid and hydroquinone derivatives was investigated. The additional functional group of the hydroquinone determines the substitution pattern and the product ratio of the phenazines formed.

Open Access June 2, 2014

Untersuchungen an quartären Pyridinium-Salzen, XV [1] Pseudobasen und Redoxprodukte bei der Umsetzung von Pyridinium-Salzen mit Alkoholat / Investigations of Quaternary Pyridinium Salts, XV [1] Pseudobases and Redox Products in the Reaction of Pyridinium Salts with Alcoxides

Wolf-H. Gündel

Page range: 873-883

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Abstract

Mono-and diquaternary pyridinium salts substituted in 3-position with electron with-drawing groups, react with alcohols under basic conditions to give 6-alcoxy-1,6-dihydro-pyridines. Symmetric dipyridinium salts react in aqueous alkaline solution to products with 6-pyridone and dihydropyridine moiety. This redox reaction depends on the length of the bridge connecting the pyridinium rings. Pyridinium salts can be reduced by aluminiumtriisopropoxide to 1,4-dihydropyridines.

Open Access June 2, 2014

In the Search for New Anticancer Drugs, III⁺ Phosphorylated Diaziridine Derivatives

George Sosnovsky, Jan Lukszo

Page range: 884-894

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Abstract

Several N-diethoxyphosphoryl derivatives 7 of various diaziridines, and compounds 12, 15a, 15b, 18 and 20, structurally related to TEPA (1a) and spin labeled Thio-TEPA (1c) were synthesized.

Open Access June 2, 2014

Heterocyelische Siebenring-Verbindungen, XXVI [1] Darstellung und photochemische Reaktion einiger substituierter 4-Phenyl-l-benzoxepine / Heterocyclic Seven-membered Ring Compounds, XXVI [1] Synthesis and Photochemical Reaction of Several 4-Phenyl-1-benzoxepins

Hans Hofmann, Rainer Heidrich, Andreas Seubert

Page range: 895-898

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Abstract

The 4-phenyl-l-benzoxepins 4, 5 and 8 have been prepared from the seven-membered diketone 1 by enol-alkylation or -acylation reactions; their photoreaction yields the corresponding 1-phenyl-2a,7 b-dihydrocyclobuta[b] l-benzofurans 9, 10 and 11.

Open Access June 2, 2014

Notizen: Einkristall-Daten der Hochdruck- Hochtemperaturphase von SrSi₂ / Single Crystal Data of the High Pressure-High Temperature Phase of SrSi₂

Jürgen Evers, Gilbert Oehlinger, Armin Weiss

Page range: 899-900

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Abstract

The high pressure-high temperature phase of SrSi 2 is a stoichiometric representative of the a-ThSi 2 type of structure. A single crystal investigation leads to interatomic distances Si-Si: 233.0(2) pm (1 x) and 248.9(2) pm (2 x), Sr-Si: 319.1(4) pm (4 x) and 334.7(4) pm (8 x), Sr-Sr: 410.8(3) pm (4 x) and 443.8(3) pm (4 x).

About this journal

Objective
Zeitschrift fuer Naturforschung B (ZNB) publishes novel research in all areas of inorganic chemistry, organic chemistry, and analytical chemistry. In particular, the journal focuses on solid state chemistry, coordination chemistry, main group element chemistry, synthetic organic chemistry, natural product chemistry and, to a lesser extent, on analytical chemistry. For more than 65 years Zeitschrift fuer Naturforschung B has been open to contributions from all fields of experimental and theoretical chemistry. Zeitschrift fuer Naturforschung B publishes 12 issues per volume/year. Sometimes double issues occur.

Topics

Solid state chemistry
Coordination chemistry
Main group element chemistry
Organic chemistry
Natural product chemistry

Article formats
Original (full) papers, research notes and preliminary communications, reports on specific research topics of current interest (reviews)

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Volume 38 Issue 7

Issue of Zeitschrift für Naturforschung B

N-Methylcarbamoylphosphate, I. Synthese / N-Methylcarbamoyl Phosphates, I. Synthesis

Abstract

Bildung von Amidophosphaten und Amidophosphorsäure aus N-Methylcarbamoylphosphaten / Formation of Amidophosphates and Amidophosphoric Acid from N-Methylcarbamoyl Phosphates

Abstract

Synthese und Struktur von N2S3Cl+SbCI6 - / Synthesis and Structure of N2S3Cl+ SbCl6-

Abstract

Bindungsverhältnisse und magnetische Eigenschaften ternärer Arsenide ET2As2 / Bonding and Magnetic Properties in Ternary Arsenides ET2As2

Abstract

31P−15N Coupling Constants and 15N/14N Isotope Effects on 31P NMR Chemical Shifts of 2-Phenylamino-2-oxo(-thioxo, -selenoxo)- 4-methyl-1,3,2-dioxaphosphorinanes and Related Compounds

Abstract

Thermoanalytische, IR-spektroskopische und quantenchemische Untersuchungen an Kristallmodifikationen des Trichlorphons / Thermo-analytical, IR-spectroscopical and Quantum-chemical Investigations on Crystal Modifications of Trichlorphone

Abstract

Coordinative Interactions in Chelated Complexes of Silicon, Part III Crystal and Molecular Structure of 1-Trichlorosilyl-1,2,3,4-tetrahydro-1,10-phenanthroline

Abstract

Interaction between Acetyltetralone and Cu(II) Ions: X-Ray Diffraction of the Ligand and Single Crystal ESR Study of the Complex

Abstract

Abstract

Abstract

Abstract

Optisch aktive Übergangsmetall-Komplexe, 84 [1] Substituenten-Effekte in Diastereomerengleichgewichten von quadratisch-pyramidalen Mo-Komplexen / Optically Active Transition Metal Complexes, 84 [1] Substituent Effects in Diastereomer Equilibria of Square-Pyramidal Mo Complexes

Abstract

Quantum Chemical Interpretation of the Photoinitiated Autoxidation of Sulphite Catalysed by Ferric Ions

Abstract

Reaktionen des Hexaphenylcarbodiphosphorans, IV [1] Reaktionen des Hexaphenylcarbodiphosphorans mit Halogenverbindungen. Diphosphaallylkationen / Reactions of Hexaphenylcarbodiphosphorane, IV [1] Reactions of Hexaphenylcarbodiphosphorane with Halogen Compounds. Diphosphaallyl Cations

Abstract

Zur Synthese von substituierten Phenazinen aus Benzofurazanoxid und Hydrochinonen [1] / Synthesis of Substituted Phenazines from Benzofurazanoxid and Hydroquinones [1]

Abstract

Untersuchungen an quartären Pyridinium-Salzen, XV [1] Pseudobasen und Redoxprodukte bei der Umsetzung von Pyridinium-Salzen mit Alkoholat / Investigations of Quaternary Pyridinium Salts, XV [1] Pseudobases and Redox Products in the Reaction of Pyridinium Salts with Alcoxides

Abstract

In the Search for New Anticancer Drugs, III+ Phosphorylated Diaziridine Derivatives

Abstract

Heterocyelische Siebenring-Verbindungen, XXVI [1] Darstellung und photochemische Reaktion einiger substituierter 4-Phenyl-l-benzoxepine / Heterocyclic Seven-membered Ring Compounds, XXVI [1] Synthesis and Photochemical Reaction of Several 4-Phenyl-1-benzoxepins

Abstract

Notizen: Einkristall-Daten der Hochdruck- Hochtemperaturphase von SrSi2 / Single Crystal Data of the High Pressure-High Temperature Phase of SrSi2

Abstract

Synthese und Struktur von N₂S₃Cl+SbCI₆ - / Synthesis and Structure of N₂S₃Cl+ SbCl₆-

Bindungsverhältnisse und magnetische Eigenschaften ternärer Arsenide ET₂As₂ / Bonding and Magnetic Properties in Ternary Arsenides ET₂As₂

³¹P−₁₅N Coupling Constants and ¹⁵N/¹⁴N Isotope Effects on ³¹P NMR Chemical Shifts of 2-Phenylamino-2-oxo(-thioxo, -selenoxo)- 4-methyl-1,3,2-dioxaphosphorinanes and Related Compounds

In the Search for New Anticancer Drugs, III⁺ Phosphorylated Diaziridine Derivatives

Notizen: Einkristall-Daten der Hochdruck- Hochtemperaturphase von SrSi₂ / Single Crystal Data of the High Pressure-High Temperature Phase of SrSi₂