Published by De Gruyter

Volume 51 Issue 3

Issue of Zeitschrift für Naturforschung B

Contents
Journal Overview

Open Access June 2, 2014

Synthese und röntgenographische Charakterisierung von zwei neuen Verbindungen des Ludwigit-Strukturtyps: Co₅Sn(BO₃)₂O₄ und Co₅Mn(BO₃ )₂O₄/Synthesis and X -Ray Characterization of Two New Compounds with Ludwigite-Structure: Co₅Sn(BO₃)₂O₄ and Co₅Mn(BO₃)₂O₄

Anne Utzolino, Karsten Bluhm

Page range: 305-308

More Download PDF

Abstract

The compounds Co 5 Sn(BO 3 ) 2 O 4 (I) and Co 5 Mn(BO 3 ) 2 O 4 (II) were prepared by using a B 2 O 3 flux technique. Single crystals were investigated by X-ray diffraction and showed orthorhombic symmetry, space group D 2h 9 -Pbam (No. 55), I a = 944.4; b = 1233.8; c = 310.5 pm; Z = 2 and II a = 925.07; b = 1241.67; c = 305.24 pm; Z = 2. Both compounds are isotypic to the mineral Ludwigite. All metal point positions show an octahedral oxygen coordination. Co 2+ and M 4+ (M = Sn or Mn) occupy one point position statistically. Both structures contain isolated, trigonal planar BO 3 units and oxygen atoms that are not coordinated to boron.

Open Access June 2, 2014

Synthese und Kristallstruktur von Dibariumzink-bis(cyclotriborat) Ba₂Zn(B₃O₆)₂/Synthesis and Crystal Structure of Di-barium Zinc Bis-cyclotriborate Ba₂Zn(B₃O₆)₂

Silke Busche, Karsten Bluhm

Page range: 309-312

More Download PDF

Abstract

Single crystals of the new compound Ba 2 Zn(B 3 O 6 ) 2 were obtained by using a B 2 O 3 flux technique. They crystallize in an as yet unknown structure type. X-ray investigations led to space group C i 1 -P1̄ (Nr.2) with lattice parameters a = 715.5(2), b = 720.5(2), c = 1178.9(4), a = 78.96(2)°, β = 85.45(2)°, γ = 60.12(1)°, Z = 2. The structure is characterized by isolated (B 3 O 6 ) 3- -rings and contains two ninefold coordinated Ba-sites. Zn 2+ is tetrahedrally coordinated by oxygen. The relation to the crystal structures of high-temperature BaB 2 O 4 and Ba 2 Ca(B 3 O 6 ) 2 is discussed.

Open Access June 2, 2014

Pb₆(AsO₄)[B(AsO₄)₄] - ein neuartiger Kristallstrukturtyp im System PbO/B₂O₃/As₂O₅ mit einem Beitrag über Pb(BAsO₅)/Pb₆(AsO₄)[B(AsO₄)₄] - a New Crystal Structure Type in the System PbO/B₂O₃/As₂O₅ with Remarks about Pb(BAsO₅)

Cheong-Hwa Park, Karsten Bluhm

Page range: 313-318

More Download PDF

Abstract

Single crystals of Pb 6 (AsO 4 )[B(AsO 4 ) 4 ] (I) and Pb(BAsO 5 ) (II) were obtained by melting B 2 O 3 , As 2 O 5 and PbO at 800 °C. X-ray investigation led to the space group (I): S 4 1 -P4̄ (Nr. 81) with a = 715.4(1), c = 976.2(3) pm, Z = 1 and (II): C 3 2 -P3 1 (Nr. 144) with a = 712.2(1), c = 693.5(2) pm, Z = 3. While (II) is isotypic to the Stillwellite structure, Pb 6 (AsO 4 )[B(AsO 4 ) 4 ] represents a completely novel type of crystal structure. Boron and arsenic are tetrahedrally coordinated by oxygen. These polyhedra form two kinds of isolated anions: AsO 4 3- and B(AsO 4 ) 4 9- . Lead is eightfold coordinated by oxygen.

Open Access June 2, 2014

Zur Synthese und Kristallstruktur von Dibariumkaliumtrizinkborat Ba₂KZn₃(B₃O₆)(B₆O₁₃)/Synthesis and Crystal Structure of Di-barium Potassium Tri-zinc Borate Ba₂KZn₃(B₃O₆)(B₆O₁₃)

Silke Busche, Karsten Bluhm

Page range: 319-324

More Download PDF

Abstract

Single crystals of the new compound Ba 2 KZn 3 (B 3 O 6 )(B 6 O 13 ) were obtained by using a B 2 O 3 flux technique; they crystallize in an as yet unknown structure type. X-ray investigations led to the space group C i 1 -P1̄ (Nr.2) with lattice parameters a = 705.2(2), b = 712.5(2), c = 1880.3(6), a = 93.43(3)°, β = 90.72(2)°, γ = 119.57(2)°, Z = 2. The structure contains (B 3 O 6 ) 3- -rings and a new discrete (B 6 O 13 ) 8- anion, which is composed of two BO 4 and two B 2 O 5 units. Zn 2+ is tetrahedrally coordinated by oxygen and two out of three tenfold coordinated Ba-sites are statistically occupied by Ba 2+ and K + .

Open Access June 2, 2014

In^III -Phthalocyanine: Darstellung, Eigenschaften und Kristallstruktur von b-Bis(triphenylphosphin)iminium-cis-di(cyanato(N))phthalocyaninato- (2-)indat(III)/ In^III Phthalocyanines: Synthesis, Properties and Crystal Structure of b-Bis(triphenylphosphine)iminium cis-Di(cyanato(N ))phthalocyaninato(2-)indate(III)

Barbara Aβmann, Andreas Franken, Heiner Homborg

Page range: 325-332

More Download PDF

Abstract

[In(Cl)Pc 2- ] reacts with bis(triphenylphosphine)iminium cyanate ((PNP)OCN) in dichloromethane to yield green-blue b (PNP) cis [In(NCO) 2 Pc 2- ] · CH 2 Cl 2 , which crystallizes in the triclinic space group P1̄ (No. 2) with Z = 2. The two cyanato(N) ligands are in a mutually cis coordination (∠ (N NCO -In -N NCO ) = 84.2(3)°). The In atom is displaced out of the plane of the four N iso atoms towards the two cyanato(N) ligands (d(In-Ct(N iso ) 4 ) = 0.988 Å). The average In-N NC0 and In-N iso bond distances are 2.16(1) and 2.216(8) Å, respectively. The N NCO -In -N NCO moiety deviates by ~ 4° from the staggered conformation relative to the In-(N iso ) 4 sceleton. Though the cyanato(N) ligands are essentially linear, there are different In-N -C angles (164.4(9) and 147.1(8)°) probably due to crystal packing effects. The Pc 2- ligand is distorted in an asymmetrically convex manner. The PNP cation adopts the bent conformation (∠(P-N(K)-P) = 143.5(6)°). The cyclic voltammogram shows three electrode processes, which are assigned to the redox pairs: Pc 3- /Pc 2- (-0.87 V) < In I /In III (-0.63 V) < Pc 2- /Pc - (0.69 V).The UV-VIS-NIR spectra and the vibrational spectra are discussed.

Open Access June 2, 2014

Zur Kenntnis zweier Formen des Zinkorthoarsenates: α-Zn₃(AsO₄)₂ und β-Zn₃(AsO₄)₂/On Two Forms of Zinc Orthoarsenate: α -Zn₃(AsO₄)₂ and β-Zn₃(AsO₄)₂

D. Frerichs, C. H. Park, Hk. Müller-Buschbaum

Page range: 333-337

More Download PDF

Abstract

Single crystals of two forms of zinc orthoarsenate (α-Zn 3 (AsO 4 ) 2 (I) and β-Zn 3 (AsO 4 ) 2 (II)) have been prepared by flux techniques. Both compounds crystallize monoclinically, space groups (I): C 2h 5 -P2 1 /c, (II): C 2h 5 -P2 1 /n, with the lattice parameters (I): a = 6.306(2), b = 8.652(2), c =1.321(4) Å, β = 92.25(5) °, Z = 4 and (II): a = 5.281(1), b = 8.494(2), c = 7.726(3) Å, β = 96.39(3)°, Z = 2. α-Zn 3 (AsO 4 ) 2 is isotypic to I-Cu 3 (AsO 4 ) 2 and β-Zn 3 (AsO 4 ) 2 to γ-Zn 3 (PO 4 ) 2 . Similarities and differences of the crystal structures are discussed.

Open Access June 2, 2014

Eine neue Verbindung im System Ba/Ln/Zn/Pt/O: Ba₄Sm₄Zn₃PtO₁₅/On a New Com pound in the System Ba/Ln/Zn/Pt/O : Ba₄Sm₄Zn₃PtO₁₅

O. Sfreddo, Ch. Rabbow, Hk. Müller-Buschbaum

Page range: 338-342

More Download PDF

Abstract

Reactions of mixtures of BaCO 3 , ZnO, Sm 2 O 3 (3:5:1) heated in platinum crucibles up to 1250 °C led to big black single crystals of Ba 4 Sm 4 Zn 3 PtO 15 . The new compound crystallizes with hexagonal symmetry, space group C 6v 4 mc, a = 11.657, c = 6,789 Å , Z = 2. It is isotypic with Ba 6 Nd 2 Al 4 O 15 but shows an ordered Pt 4+ and Zn 2+ distribution over the aluminium positions. The octahedrally coordinated barium sites of the Ba 6 Nd 2 Al 4 O 15 type are occupied by Sm 3+ . In comparison to compounds of the composition Ba 6 Ln 2 M 4 O 15 (M = Al, Fe, Co), Ba 4 Sm 4 Zn 3 PtO 15 is the first example containing different oxidation states at the M 3+ positions.

Open Access June 2, 2014

Zur Kenntnis eines Barium-Lanthanoid-Aluminat-Zinkats: BaLuAlZn₃O₇ mit einem Anhang zu Ba₂Er₂Zn₈O₁₃/On a Barium Rare Earth Aluminate Zincate: BaLuAlZn₃O₇ with a Note on Ba₂Er₂Zn₈O₁₃

Ch. Rabbow, Hk. Müller-Buschbaum

Page range: 343-347

More Download PDF

Abstract

Reactions of BaCO 3 , ZnO, Lu 2 O 3 and Al 2 O 3 mixtures at temperatures up to 1500 °C led to small and colourless rods of BaLuAlZn 3 O 7 . The new compound crystallizes with hexagonal symmetry, space group C 6v 4 -P6 3 mc, a = 6.273, c =10.161 Å, Z = 2. In spite of small differences in the oxygen content BaLuAlZn 3 O 7 is isotypic to Ba 2 Ln 2 Zn 8 O 13 . The crystal structure shows Zn 2+ with tetrahedral, Lu 3+ with octahedral and Ba 2+ with anticuboctahedral coordination by O 2- . It has been shown that parts of the [Zn 3 AlO 7 ] 5- network are fragments of the ZnO structure. In consequence one oxygen atom is fourfold coordinated by zinc/aluminium. The space group of Ba 2 Ln 2 Zn 8 O 13 must be corrected to C 6v 4 -P6 3 mc.

Open Access June 2, 2014

Synthese und [4+2]-Cycloadditionen von 4a, 8a-Methanophthalazin, das erste Propellan mit einem elektronenreichen und einem elektronenarmen 4π-Diensystem/Synthesis and [4+2] Cycloaddition Reactions of 4a, 8a-Methanophthalazine, the First Propellane with an Electronrich and an Electrondeficient 4π-Diene System

Jörg Laue, Gunther Seitz, Hans Waßmuth

Page range: 348-358

More Download PDF

Abstract

Cyclopropabenzene 3 reacts with 3,6-bis(trifluoro)-1,2,4,5-tetrazine 4 to afford in high yield the 4a,8a-methanophthalazine 6, the first propellane, containing an electron rich cyclohexadiene system on the one hand and an electron deficient diazadiene system on the other hand. According to the principle of Diels-Alder reactions with inverse electron demand, electron rich dienophiles like ketene acetals, enamines or dimethyl hydrazones react predominantly with the diazadiene system to yield the azo-bridged cycoadducts of type 19 and/or the tricyclic tetrahydropyridazines like 20. In the same fashion several more or less angle strained cycloalkenes cycloadd to the diazadiene of the propellane 6 to give the novel polycyclic azo compounds 34, 36, 38,40, 42 and 44 with exo-configuration of the annulated cycloalkanes. Attack apparently occurs from less hindered face anti to the methano bridge of 6 with high stereo-and site-selectivity. As anticipated the electron deficient dienophiles 1,2,4-triazoline-3,5-dione 45 and the benzoquinone 46 add with different site selectiviy to 6 furnishing the polycyclic pyridazines 47 and 48 resp. again by exclusive anti attack. Treatment of 6 with both an electron rich and an electron deficient dienophile like 49 and 45 resp. affords the heptacyclic anti-anti-bis adduct 51 with analogously high site-and stereoselectivity.

Open Access June 2, 2014

Darstellung, ¹¹B-, ¹³C-, ¹H-NMR - und Schwingungsspektren von μ-Pentamethylen-bis-hexahydro-closo-hexaborat, [B₆H₆(CH₂)₅B₆H₆]^2-, und μ-Hexamethylen-bis-hexahydro-closo-hexaborat, [B₆H₆(CH₂)₆B₆H₆]₂/Preparation, ¹¹B, ¹³C, ¹H NMR and Vibrational Spectra of μ-Pentamethylene-bis-hexahydro-closo-hexaborate, [B₆H₆(CH₂)₅ B₆H₆ ]^2-, and μ-Hexamethylene-bis-hexahydro-closo-hexaborate, [B₆H₆(CH₂)₆B₆H₆]^2-

W. Lübbe, W. Preetz

Page range: 359-362

More Download PDF

Abstract

In the reaction of [B 6 H 6 ] 2- with diiodopentane or diiodohexane in dichloromethane μ-pentamethylene-bis-hexahydro-closo-hexaborate, [B 6 H 6 (CH 2 ) 5 B 6 H 6 ] 2- (I), and μ-hexamethylene-bishexahydro-closo-hexaborate, [B 6 H 6 (CH 2 ) 6 B 6 H 6 ] 2- (II), are formed, respectively. The products were separated from excess [B 6 H 6 ] 2- by ion exchange chromatography on diethylaminoethyl cellulose and have been identified and characterized by 11 B, 13 C, 1 H NMR and vibrational spectroscopy.

Open Access June 2, 2014

Darstellung, ¹¹B-, ¹³C-, ¹H-NMR- und Schwingungsspektren von μ-Dimethylen-bis-hexahydro-closo-hexaborat, [B₆H₆(CH₂)₂B₆H₆]^2-, sowie Kristallstrukturen von [As(C₆H₅)₄]₂[B₆H₆(CH₂)₂B₆H₆]·[(CH₃)₂CO] und [P(C₆H₅)₄]₂[B₆H₆(CH₂)₂B₆H₆]·[C₂H₅OH]/Preparation, ¹¹B , ¹³C, ¹H NMR and Vibrational Spectra of μ-Dimethylene-bis-hexahydro-closo-hexaborate, [B₆H₆(CH₂)₂B₆H₆]^2- , and the Crystal Structures of [As(C₆H₅)₄]₂[B₆H₆(CH₂)₂B₆H₆]·[(CH₃)₂CO] and [P(C₆H₅)₄]₂[B₆H₆(CH₂)₂B₆H₆]·[C₂H₅OH]

W. Lübbe, W. Preetz

Page range: 363-369

More Download PDF

Abstract

By reaction of [B 6 H 6 ] 2- with dibromoethane in acetonitrile μ-dimethylene-bis-hexahydro-closo-hexaborate(2-), [B 6 H 6 (CH 2 ) 2 B 6 H 6 ] 2- , is formed. The compound was separated from excess [B 6 H 6 ] 2- by ion exchange chromatography on diethylaminoethyl cellulose. The crystal structures of [As(C 6 H 5 ) 4 ] 2 [B 6 H 6 (CH 2 ) 2 B 6 H 6 ]·[(CH 3 ) 2 CO] (I) and [P(C 6 H 5 ) 4 ] 2 [B 6 H 6 (CH 2 ) 2 B 6 H 6 ]·[C 2 H 5 OH] (II) have been determined by single crystal X-ray analysis: I is triclinic, space group P1̄ with a = 10.264(2), b = 13.804(2) and c = 20.242(2) Å, α = 97.857(10)°, β = 92.734( 11)° and γ = 103.024( 13)°; II is monoclinic, space group P2 1 /n with a = 12.742(2), b = 7.532(2) and c = 26.887(3) Å, β = 95.765( 10)°. The 11 B NMR spectrum of this compound reveals the feature of monosubstituted octahedral B 6 cages. The 13 C NMR spectrum exhibits a triplet at 16.20 ppm with 1 J(C,H) = 120.4 Hz. In the 1 H NMR spectrum a singulet at 0.72 ppm of the CH 2 -groups and two singulets at 1.72 and -4.95 ppm of the BH fragments are observed. The IR and Raman spectra exhibit strong CH stretching bands between 2908 and 2789 cm -1 , BH stretching bands between 2463 and 2396 cm -1 , and the BC stretching vibration at 1144 in the IR and at 1150 cm -1 in the Raman spectrum.

Open Access June 2, 2014

Synthese und Dimerisierungsverhalten des 1,1-Bis(trimethylsilyl)-2-(2,5-diisopropylphenyl)silens/ Synthesis and Dimerization Behavior of 1,1 -Bis(trimethylsilyl)-2-(2,5-diisopropylphenyl)silene

Douglas Hoffmann, Helmut Reinke, Hartmut Oehme

Page range: 370-376

More Download PDF

Abstract

Tris(trimethylsilyl)silylmagnesium bromide, (Me 3 Si) 3 SiMgBr, reacts with 2.5-diisopropylbenzaldehyde to give 2,5-diisopropylphenyl-tris(trimethylsilyl)silylmethanol (1). With sodium hydride in THF compound 1 undergoes a rearrangement through 1,3-Si,O-trimethylsilyl migration affording bis(trimethylsilyl)silyl-(2,5-diisopropylphenyl)-trimethylsiloxy-methane (4). The deprotonation of 1 with organolithium reagents in ether leads to the elimination of lithium trimethylsilanolate according to a modified Peterson mechanism resulting in the formation of the transient silene (Me 3 Si) 2 Si=CH(2,5-iPr 2 C 6 H 3 ) (2). Treatment of 1 with an excess of phenyllithium in diethylether at low temperature gives 1,1,1,3,3,3-hexamethyl-2- phenyl-2-(2,5-diisopropylbenzyl)-trisilane (3), formed in a nucleophilic addition of the excess PhLi to the silene intermediate and in the hydrolytic workup. Stochiometric quantities of MeLi in diethylether at -78 °C convert compound 1 into a head-to-head dimer of the silene 1,2,3,8a-tetrahydro-5,8-diisopropyl-1 -(2,5-diisopropylphenyl)-2,2,3,3-tetrakis-(trimethylsilyl)- 2,3-disilanaphthalene (5). Compound 5, presumably the kinetically preferred product of the cyclodimerization of 2, gradually transforms into the thermodynamically stable 3,4-bis(2,5- diisopropylphenyl)-1, 1,2,2-tetrakis(trimethyl-silyl)-1,2-disilacyclobutane (6). The E/Z-isomers of 6 have been characterized by X-ray crystal structural analyses.

Open Access June 2, 2014

2,5,8,11-Tetra-tert-butyl-peri-xanthenoxanthene and its Dication Spectroelectrochemistry and Model Calculations on a Dioxa-22-π-system

Gernot Frenking, Anton Rieker, Josef Salbeck, Bernd Speiser

Page range: 377-380

More Download PDF

Abstract

Spectroelectrochemistry of 2,5,8,1 1-tetra-tert-butyl-peri-xanthenoxanthene 1 yields the UV/VIS spectra of the corresponding radical cation 1 + and dication 1 2+ . The bathochromic shift for the dication 1 2+ relative to 1 and to the isoelectronic hydrocarbon anthanthrene (2) can be understood by quantum mechanical calculations (ab initio, AM1) of model structures.

Open Access June 2, 2014

1,4-Addition of Lithium Organyls to para-Quinols / Structure Determination of 2,6-Di-tert-butyl-4-hydroxy-4,5-diphenylcyclohex-2-en-1-one

Gerhard Henes, Anton Rieker, Markus Neumayer, Wolfgang Hiller

Page range: 381-387

More Download PDF

Abstract

Addition of lithium organyls to sterically hindered para-quinols leads to 1,2-or 1,4-adducts. The 1,4-addition prevails, if the 4-substituents in the quinol and the organic group in the lithium organyl are large. Four 1,4-addition products (2-cyclohex-2-en-1-ones) are synthesized and their structures investigated by NMR spectroscopy. The aryl groups at C-4 and C-5 acquire equatorial positions, the alkyl group at C-6 is bisectional. These results are confirmed by X-ray analysis of 2,6-di-tert-butyl-4-hydroxy-4,5-diphenylcyclohex-2-en-1 -one, revealing a twist boat conformation of the cyclohexene ring.

Open Access June 2, 2014

Electrochemistry of Oxygenation Catalysts, Part 6 Electrosynthesis, Structure, Analytical and Electrochemical Properties of Monomeric [Co^III(salen)(DMF)₂]⁺ X^- Salts (X = PF₆, ClO₄)

Bernhard Gollas, Bernd Speiser, Hartmut Stahl, Jürgen Sieglen, Joachim Strähle

Page range: 388-398

More Download PDF

Abstract

[Co III (salen)(DMF) 2 ] + X - salts [X = PF 6 , ClO 4 ; salen = bis(salicyliden)ethylendiiminato; DMF = dimethylformamide] have been synthesized by electrochemical and chemical (air) oxidation of Co II (salen). Their monomeric structure with two DMF molecules in the axial positions in both the solid state and DMF solution is shown by X-ray crystal structure analysis, thermal analysis, mass spectroscopy, and 1 H and 13 C NMR spectroscopy. The electrochemical reduction of the [Co III (salen)(DMF) 2 ] + cation is investigated by cyclic voltammetry and com pared to the oxidation of the neutral Co II (salen). The redox reaction connecting the cobalt(II) and the cobalt(III) species appears to be a quasi-reversible electron transfer. These properties make the [Co III (salen)(DMF) 2 ] + X - salts starting materials for the analysis of the interaction of basic substrates with cobalt(III) species in the context of the biomimetic oxygenation reactions catalyzed by such complexes.

Open Access June 2, 2014

Verknüpfung koordinativ ungesättigter Kupfer(II)-Monomere via Cyano-versus Tetrazolyl-Donor/ Linkage of Coordinatively Unsaturated Copper(II) Monomers via Cyano versus Tetrazolyl Donor

Rolf W. Saalfrank, Roland Harbig, Oliver Struck, Eva-Maria Peters, Hans Georg von Schnering

Page range: 399-408

More Download PDF

Abstract

Reaction of a methanolic copper(II) acetate solution with tetrazolyl enol derivatives 2a (HL 2 ) or 2b (HL 3 ) leads to the formation of the corresponding 2D-coordination polymers 4 ( ∞ 2 [CuL 2 2 ]) and 5 ( ∞ 2 [CuL 2 3 ]), respectively. Single-crystal X-ray diffraction of the supramolecular species 4 and 5 established unequivocally the structures of the regioisomeric coordination polymers. On the contrary, reactions of 2c (HL 4 ) with methanolic copper(II) acetate solution and 2b (HL 3 ) with methanolic zinc(II) acetate solution yield mononuclear chelate complexes 11 ([CuL 4 2 ]) and 12 ([ZnL2 3 (MeOH) 2 ]). The structures of 11 and 12 have been established by X-ray structure analysis.

Open Access June 2, 2014

Reduktion cyclischer Maleinsäurederivate/Reduction of Cyclic Maleic Acid Derivatives

Hans-Dietrich Stachel, Josef Schachtner, Josef Seidel

Page range: 409-416

More Download PDF

Abstract

A series of potentially cytotoxic α,β-unsaturated γ -hydroxy-butyrolactones, -lactams and -thiolactones has been synthesized via regioselective hydride reduction of the appropriate maleic acid anhydrides, imides and thioanhydrides. By this means a straightforward access to naturally occurring antibiotic narthigenine 2, its hitherto unknown thio-analogue 5b and higher substituted derivatives and analogues of 2 is presented.

Open Access June 2, 2014

Electroreduction of Organic Compounds, 27 Electrochemical Dehalogenation of Endosulfane

J. Gassmann, J. Voss, G. Adiwidjaja

Page range: 417-420

More Download PDF

Abstract

Partial dechlorination takes place if Endosulfane ® is electrolysed in methanol solution at lead cathodes. The products are detected and identified by GC/MS, IR and NMR spectroscopy. The structure of the product 2 is confirmed by an X-ray structural analysis.

Open Access June 2, 2014

Vinamidinium-Salze als Nucleophile Vinamidinium Salts as Nucleophiles

H. Möhrle, U. von der Lieck-Waldheim

Page range: 421-430

More Download PDF

Abstract

2,3-Dihydro-1,4-diazepinium salts could not be aminomethylated with conventional methods, but the hydrochlorides produced with methyleniminium salts the C-Mannich-compounds. The reactivity of the substrate was mainly controlled by electronic effects of the substituents. Aminomethylation of 1,5-diazapentadienium salts occurred only if the conformations caused no steric hindrance of the β-C-atom. Methyl substituted 2,3-dihydro-1,4-diazepinium salts reacted with 1,3,5 triazine to pyrimidine anellated derivatives.

Open Access June 2, 2014

Notizen:1,3-Dimethoxy-6H- benzo[b]naphtho[1,2-d]pyran-6-thione, a Thionolactone-Bridged Axially Prostereogenic Biaryl

Karl Peters, Eva-Maria Peters, Gerhard Bringmann, Olaf Schupp

Page range: 431-432

More Download PDF

Abstract

The title compound was prepared from the corresponding “ordinary” oxolactone bridged biaryl using Lawesson’s reagent. It crystallizes from dichloromethane / petroleum ether in the monoclinic system, space group P2 1 /a; a = 1115.7(2),b = 1383.9(2), c = 1042.0(1) pm and β = 106.67(1)°.

Open Access June 2, 2014

[Mn(n-Bu)(NPEt₃)]₄, eine manganorganische Verbindung mit Heterocuban -Struktur [Mn(n-Bu)(NPEt₃)]₄, an Organomanganese Compound with Heterocubane Structure

Hans-Joachim Mai, Bernhard Neumüller, Kurt Dehnicke

Page range: 433-436

More Download PDF

Abstract

[Mn (n- Bu)(NPEt 3 )] 4 has been prepared by the reaction of [MnBr(NPEt 3 )] 4 with n-butyllithium in boiling pentane. The pyrophoric compound forms red, moisture sensitive crystals, which were characterized by IR spectroscopy and by a crystal structure determination (tetragonal, space group 14 1 /a, Z = 4, structure solution with 699 observed unique reflections, R = 0.054. Lattice dimensions at -50 °C:a = b = 2177.4(3) pm, c = 1147.1(2) pm). [Mn (n-Bu)(NPEt 3 )] 4 forms a nearly perfect Mn 4 N 4 hetero cubane framework with μ 3 -N bridges of the NPEt 3 - groups and σ-bonded n-butyl groups with Mn - C distances of 216.8 pm. The n-butyl groups and two of the ethyl groups are disordered.

Open Access June 2, 2014

Novel Enantiomerically Pure Ferrocenes

Adolphus A . H. van der Zeijden, J. Sieler, E. Hovestreydt

Page range: 437-440

More Download PDF

Abstract

A chiral ferrocene (Cp E 2 Fe) was synthesized by reaction of Cp E Li with FeCl 2 (THF) 1.5 The cyclopentadienyl ligand Cp E contains a dimethylamino group that is separated from the Cp backbone by two stereogenic carbon centres. Reaction of Cp E 2 Fe with excess Mel affords the ammonium salt Cp E 2 Fe.2MeI. Its solid state structure was determined by X-ray diffraction methods.

Open Access June 2, 2014

The Crystal Structure of β-CsIO₄, the Room-Temperature Modification of Cesium Periodate

Danita de Waal, Manfred Zabel, Klaus-Jürgen Range

Page range: 441-443

More Download PDF

Abstract

The crystal structure of β-CsIO 4 , the room-temperature modification of cesium periodate, was determined as orthorhombic, space group Pnma, with a = 5.8644(5), b = 6.0326(4), c = 14.379(1) A and Z = 4. The structure was refined to R 1 = 0.0309, wR 2 = 0.0701 for 425 absorption-corrected reflections. β-CsIO 4 is isostructural with β-CsReO 4 . The structure comprises isolated IO 4 tetrahedra, linked together by Cs ions. The average I-O distance was found to be 1.747 Å .

Open Access June 2, 2014

Strukturverfeinerung von Kalium - periodat bei 297 und 150 K/Structure Refinement of Potassium Periodate at 297 and 150 K

Danita de Waal, Klaus-Jürgen Range

Page range: 444-446

More Download PDF

Abstract

The scheelitetype structure of potassium periodate, KIO 4 , has been confirmed and refined from single-crystal X-ray data at two temperatures. The compound crystallizes tetragonally, space group I4 1 /a, with a = 5.726(1), c = 12.607(4) Å at 297(1) K, and a = 5.704(3), c = 12.478(8) Å at 150(1) K, respectively. Except for a significant decrease in the anisotropic displacement factors, the changes in the structural parameters at low temperature are rather small.

Open Access June 2, 2014

Zur Kristallstruktur von ( Cu ,Mn )_3,66Mo₃O₁₂/On the Crystal Structure of (Cu ,Mn)_3,66Mo₃O₁₂

O. Sedello, Hk. Müller-Buschbaum

Page range: 447-449

More Download PDF

Abstract

Single crystals of (Cu,Mn) 3.66 Mo 3 O 12 have been prepared in sealed copper tubes. X-ray investigations lead to orthorhombic symmetry, space group D 2h 16 -Pnma, a = 5.1541(9), b = 10.788(2), c = 18.114(3)) Å , Z = 4. (Cu,Mn) 3.66 Mo 3 O 12 is isotypic to NaCo 2.31 Mo 3 O 12 and (Cu,Co) 3.75 Mo 3 O 12 with split positions for two of the metals.

Open Access June 2, 2014

Zur Kristallstruktur von ( Cu , Mn ) UMo₃O₁₂/On the Crystal Structure of (Cu, Mn )UMo₃O₁₂

Page range: 450-452

More Download PDF

Abstract

Single crystals of (Cu,Mn)UMo 3 O 12 have been prepared in sealed copper tubes. X-ray investigations lead to hexagonal symmetry, space group C 6h 2 -P6 3 /m a = 9.7895 (13), c = 6.202(1) Å , z = 2. (Cu,Mn)UMo 3 O 12 is isotypic to CdThMo 3 O 12 . Calculations of the Coulomb terms of lattice energy with respect to different oxidation states of copper, molybdenum and uranium and the previously described pair of isotypic compounds of CdThMo 3 O 12 to Na 2 ThRe 6 O 24 are discussed.

Open Access June 2, 2014

Zur Kenntnis von Ba₆Pr₂Co₄O₁₅ und Ba₅SrPr₂Co₄O₁₅ On Ba₆Pr₂Co₄O₁₅ and Ba₅SrPr₂Co₄O₁₅

Hk. Müller-Buschbaum, H. Ünsal

Page range: 453-456

More Download PDF

Abstract

Ba 6 Pr 2 Co 4 O 15 (I) and Ba 5 SrPr 2 Co 4 O 15 (II) have been prepared by high temperature CO 2 -LASER techniques. Both compounds crystallize with hexagonal symmetry, space group C 6v 4 P6 3 mc, (I): a = 11.814(1), c = 7.100(2) Å ; (II): a = 11.646(1), c = 6.8602 Å , Z = 2. It is remarkable that the strongly reducing Pr 3+ can coexist with the more oxidizing Co 3+ .

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)

> Information on submission process

Volume 51 Issue 3

Issue of Zeitschrift für Naturforschung B

Synthese und röntgenographische Charakterisierung von zwei neuen Verbindungen des Ludwigit-Strukturtyps: Co5Sn(BO3)2O4 und Co5Mn(BO3 )2O4/Synthesis and X -Ray Characterization of Two New Compounds with Ludwigite-Structure: Co5Sn(BO3)2O4 and Co5Mn(BO3)2O4

Abstract

Synthese und Kristallstruktur von Dibariumzink-bis(cyclotriborat) Ba2Zn(B3O6)2/Synthesis and Crystal Structure of Di-barium Zinc Bis-cyclotriborate Ba2Zn(B3O6)2

Abstract

Pb6(AsO4)[B(AsO4)4] - ein neuartiger Kristallstrukturtyp im System PbO/B2O3/As2O5 mit einem Beitrag über Pb(BAsO5)/Pb6(AsO4)[B(AsO4)4] - a New Crystal Structure Type in the System PbO/B2O3/As2O5 with Remarks about Pb(BAsO5)

Abstract

Zur Synthese und Kristallstruktur von Dibariumkaliumtrizinkborat Ba2KZn3(B3O6)(B6O13)/Synthesis and Crystal Structure of Di-barium Potassium Tri-zinc Borate Ba2KZn3(B3O6)(B6O13)

Abstract

Abstract

Zur Kenntnis zweier Formen des Zinkorthoarsenates: α-Zn3(AsO4)2 und β-Zn3(AsO4)2/On Two Forms of Zinc Orthoarsenate: α -Zn3(AsO4)2 and β-Zn3(AsO4)2

Abstract

Eine neue Verbindung im System Ba/Ln/Zn/Pt/O: Ba4Sm4Zn3PtO15/On a New Com pound in the System Ba/Ln/Zn/Pt/O : Ba4Sm4Zn3PtO15

Abstract

Zur Kenntnis eines Barium-Lanthanoid-Aluminat-Zinkats: BaLuAlZn3O7 mit einem Anhang zu Ba2Er2Zn8O13/On a Barium Rare Earth Aluminate Zincate: BaLuAlZn3O7 with a Note on Ba2Er2Zn8O13

Abstract

Abstract

Abstract

Abstract

Synthese und Dimerisierungsverhalten des 1,1-Bis(trimethylsilyl)-2-(2,5-diisopropylphenyl)silens/ Synthesis and Dimerization Behavior of 1,1 -Bis(trimethylsilyl)-2-(2,5-diisopropylphenyl)silene

Abstract

2,5,8,11-Tetra-tert-butyl-peri-xanthenoxanthene and its Dication Spectroelectrochemistry and Model Calculations on a Dioxa-22-π-system

Abstract

1,4-Addition of Lithium Organyls to para-Quinols / Structure Determination of 2,6-Di-tert-butyl-4-hydroxy-4,5-diphenylcyclohex-2-en-1-one

Abstract

Electrochemistry of Oxygenation Catalysts, Part 6 Electrosynthesis, Structure, Analytical and Electrochemical Properties of Monomeric [CoIII(salen)(DMF)2]+ X- Salts (X = PF6, ClO4)

Abstract

Verknüpfung koordinativ ungesättigter Kupfer(II)-Monomere via Cyano-versus Tetrazolyl-Donor/ Linkage of Coordinatively Unsaturated Copper(II) Monomers via Cyano versus Tetrazolyl Donor

Abstract

Reduktion cyclischer Maleinsäurederivate/Reduction of Cyclic Maleic Acid Derivatives

Abstract

Electroreduction of Organic Compounds, 27 Electrochemical Dehalogenation of Endosulfane

Abstract

Vinamidinium-Salze als Nucleophile Vinamidinium Salts as Nucleophiles

Abstract

Notizen:1,3-Dimethoxy-6H- benzo[b]naphtho[1,2-d]pyran-6-thione, a Thionolactone-Bridged Axially Prostereogenic Biaryl

Abstract

[Mn(n-Bu)(NPEt3)]4, eine manganorganische Verbindung mit Heterocuban -Struktur [Mn(n-Bu)(NPEt3)]4, an Organomanganese Compound with Heterocubane Structure

Abstract

Novel Enantiomerically Pure Ferrocenes

Abstract

The Crystal Structure of β-CsIO4, the Room-Temperature Modification of Cesium Periodate

Abstract

Strukturverfeinerung von Kalium - periodat bei 297 und 150 K/Structure Refinement of Potassium Periodate at 297 and 150 K

Abstract

Zur Kristallstruktur von ( Cu ,Mn )3,66Mo3O12/On the Crystal Structure of (Cu ,Mn)3,66Mo3O12

Abstract

Zur Kristallstruktur von ( Cu , Mn ) UMo3O12/On the Crystal Structure of (Cu, Mn )UMo3O12

Abstract

Zur Kenntnis von Ba6Pr2Co4O15 und Ba5SrPr2Co4O15 On Ba6Pr2Co4O15 and Ba5SrPr2Co4O15

Abstract

Synthese und röntgenographische Charakterisierung von zwei neuen Verbindungen des Ludwigit-Strukturtyps: Co₅Sn(BO₃)₂O₄ und Co₅Mn(BO₃ )₂O₄/Synthesis and X -Ray Characterization of Two New Compounds with Ludwigite-Structure: Co₅Sn(BO₃)₂O₄ and Co₅Mn(BO₃)₂O₄

Synthese und Kristallstruktur von Dibariumzink-bis(cyclotriborat) Ba₂Zn(B₃O₆)₂/Synthesis and Crystal Structure of Di-barium Zinc Bis-cyclotriborate Ba₂Zn(B₃O₆)₂

Pb₆(AsO₄)[B(AsO₄)₄] - ein neuartiger Kristallstrukturtyp im System PbO/B₂O₃/As₂O₅ mit einem Beitrag über Pb(BAsO₅)/Pb₆(AsO₄)[B(AsO₄)₄] - a New Crystal Structure Type in the System PbO/B₂O₃/As₂O₅ with Remarks about Pb(BAsO₅)

Zur Synthese und Kristallstruktur von Dibariumkaliumtrizinkborat Ba₂KZn₃(B₃O₆)(B₆O₁₃)/Synthesis and Crystal Structure of Di-barium Potassium Tri-zinc Borate Ba₂KZn₃(B₃O₆)(B₆O₁₃)

Zur Kenntnis zweier Formen des Zinkorthoarsenates: α-Zn₃(AsO₄)₂ und β-Zn₃(AsO₄)₂/On Two Forms of Zinc Orthoarsenate: α -Zn₃(AsO₄)₂ and β-Zn₃(AsO₄)₂

Eine neue Verbindung im System Ba/Ln/Zn/Pt/O: Ba₄Sm₄Zn₃PtO₁₅/On a New Com pound in the System Ba/Ln/Zn/Pt/O : Ba₄Sm₄Zn₃PtO₁₅

Zur Kenntnis eines Barium-Lanthanoid-Aluminat-Zinkats: BaLuAlZn₃O₇ mit einem Anhang zu Ba₂Er₂Zn₈O₁₃/On a Barium Rare Earth Aluminate Zincate: BaLuAlZn₃O₇ with a Note on Ba₂Er₂Zn₈O₁₃

Electrochemistry of Oxygenation Catalysts, Part 6 Electrosynthesis, Structure, Analytical and Electrochemical Properties of Monomeric [Co^III(salen)(DMF)₂]⁺ X^- Salts (X = PF₆, ClO₄)

[Mn(n-Bu)(NPEt₃)]₄, eine manganorganische Verbindung mit Heterocuban -Struktur [Mn(n-Bu)(NPEt₃)]₄, an Organomanganese Compound with Heterocubane Structure

The Crystal Structure of β-CsIO₄, the Room-Temperature Modification of Cesium Periodate

Zur Kristallstruktur von ( Cu ,Mn )_3,66Mo₃O₁₂/On the Crystal Structure of (Cu ,Mn)_3,66Mo₃O₁₂

Zur Kristallstruktur von ( Cu , Mn ) UMo₃O₁₂/On the Crystal Structure of (Cu, Mn )UMo₃O₁₂

Zur Kenntnis von Ba₆Pr₂Co₄O₁₅ und Ba₅SrPr₂Co₄O₁₅ On Ba₆Pr₂Co₄O₁₅ and Ba₅SrPr₂Co₄O₁₅