Published by De Gruyter

Volume 51 Issue 6

Issue of Zeitschrift für Naturforschung B

Contents
Journal Overview

Open Access June 2, 2014

Metallkomplexe von N-(Pyrrol-l-yl)salicylaldiminen und deren Strukturbestimmung mittels Röntgendiffraktometrie und Röntgenabsorptionsspektroskopie (XANES) / Metal Chelates of N -(Pyrrol-l-yl)salicylaldim ines and their Structure D eterm ination by X-Ray Structure Analysis and X -R ay Absorption Spectroscopy (XANES)

A. Bach, L. Beyer, T. Gelbrich, K. H. Hallmeier, C. Hennig, M. Möbius, R. Richter, R. Szargan, V. Fernandez, J. Losada

Page range: 757-764

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Abstract

A series of three N-(pyrrol-l-yl)salicylaldim ines 1-3 has been prepared an d characterized. Their metal chelate complexes with Cu, Ni and Co are described. The molecular structures of bis[N-(pyrrol-l-yl)salicylaldim inato]copper(lI) la, bis{N-[3-(pyrrol-l-yl)propyl]- salicylaldiminato}nickel(II) 2b and tris{N-[3-(pyrrol-l-yl)propyl]salicylaldiminato}cobalt(III) 2d were determined by X-ray structure analysis. The chelates with tetracoordinated copper and nickel show a square planar coordination with the characteristic trans configuration. The chelate with hexacoordinated cobalt has a meridional coordination sphere. The complexes have also been investigated by X-ray absorption spectroscopy (X̲-ray A̲bsorption N̲ear E̲dge S̲tructure, XANES) at the K edges of the 3d metals. Analyzing the relative intensities of the Is → 3d prepeak and the K edges of the line shape, it was possible to distinguish between planar, tetrahedral and octahedral coordination of the chelates

Open Access June 2, 2014

Polynuclear Gold(I) Complexes of Mercaptocarboxylic Acids

Alexander Sladek, Wolfgang Schneider, Klaus Angermaier, Andreas Bauer, Hubert Schmidbaur

Page range: 765-772

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Abstract

In a search for air-stable and water-soluble mercapto compounds of gold with a high gold content, benzylthiol, a-m ercapto-acetic acid, β-mercapto-propionic acid, and thiosalicylic acid were converted into aurated sulfonium salts by treatment with reagents of the type [(R 3 P)Au] 3 O + BF 4 - or [(R 3 )P)Au] + BF 4 - . - BzSH served as a mono-functional model thiol, which was converted into BzS[Au(PMe 3 )] 2 + BF 4 - (1). The small tertiary phosphine was chosen in order to minimize steric effects. In the crystal the cations are associated into centrosymmetrical dimers through short Au-A u contacts (auriophilicity). - The two carboxylic acids with thiol functions, HSCH 2 COOH and HSCH 2 CH 2 COOH, gave triply aurated species of the type {[(Ph 3 P)Au] 2 S(CH 2 )nCOOAu(PPh 3 )} + BF 4 - (2: n = 2, 3; n = 3). The crystal structure analysis of the representative compound 2 showed again the presence of centrosymmetrical cation dimers with geometrical details of the sulfonium part of the molecules very similar to those of the reference compound 1. In addition, the carboxyl groups in 2 and 3 bear a (phosphine)gold unit mono-hapto bound at one of the oxygen atoms. -2-HS-C 6 H 4 -COOH was converted into a sulfonium salt {[(Ph 3 P)Au] 2 S-C 6 H 4 -COOH} + BF 4 - (4), which crystallizes free of solvent from dry dichloromethane, and as a monohydrate with one mole of dichloromethane (4a = 4 H 2 O-CH 2 CI 2 ) from hydrous CH 2 CI 2 . In the solvent-free crystalline phase (4) the cations are associated into dimers with the usual intermolecular double A u-A u contacts, but in 4a there are monomeric cations with the water molecule hydrogen-bonded to the carboxylic acid function

Open Access June 2, 2014

Phosphonio-substituierte 1,3-Diphosphanaph thaline aus der a,o-Kondensation von Phosphonium-benzyliden / Phosphonio-Substituted 1,3-Diphosphanaphthalenes from the α.o-Condensation of Phosphonium-benzylides

Georg Jochem, Alfred Schmidpeter

Page range: 773-777

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Abstract

Triphenylphosphonium 1-trimethylsilylbenzylides 1 react with the bis(dichlorophosphino)- substituted ylide 2 both at their 1- and ortho-position to yield 1,3-diphosphatetraline derivatives 4 containing two ylide and PCI units each as alternating ring members. The two PCI groups differ decisively in their spontaneous dissociation in a polar medium, as well as in their oxidation by elemental sulfur. With gallium trichloride dicationic 1,3-diphosphanaphthalenes (1,3-benzodiphosphinines) are formed, in which both phosphorus ring members achieve twocoordination and which represent a novel π 10 system

Open Access June 2, 2014

Reaktive E=C(p-p)π-Systeme, XLIII [1] Darstellung und Charakterisierung P-Phosphino- oder P-Arsino-substituierter Fluorphosphaalkene des Typs R₂E-P=C(F)NEt₂ (R = Me, CF₃, Me₂N; E = P, As) / Reactive E=C(p-p)-π Systems XLIII [1] Synthesis and Characterization of P-Phosphino or P-Arsino Substituted Fluorophosphaalkenes of the Type R₂E-P=C(F)NEt₂ (R= Me, CF₃, Me₂N; E = P As)

Joseph Grobe, Duc Le Van, Jost Winnemöller, Bernt Krebs, Mechtild Läge

Page range: 778-784

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Abstract

The easily accessible phosphaalkene HP=C(F)NEt 2 (lb) reacts with halophosphanes or -arsanes R 2 EX (X = Cl, I) in the presence of NEt 3 to give P-phosphino- or -P-arsino substituted fluorophosphaalkenes of the type RiE-P=C(F)NEti (2 - 6) in high yields (60 - 85 %) [R 2 E: (CF 3 ) 2 P (2), Me 2 N(CF 3 )P (3), Me 2 P (4), (CF 3 ) 2 As (5), Me 2 As (6)]. The analogous reaction of ib with CF 3 PI 2 (molar ratio 1:2) unexpectedly leads to the triphosphetene Et 2 N - C=P-PCF 3 -PCF 3 (7). The stability of compounds 2 - 6 as a function of R 2 E decreases from As to P and from CF 3 to Me, respectively. Compounds 2 - 6 generally show the Z-configuration and have been characterized by thorough spectroscopic investigations (MS,IR; 1 H, 19 F, 11 C, 31 PNMR). A single crystal X-ray diffraction study of 2 proves the π-type interaction of the nitrogen lone pair with the P=C bond thus enhancing the stability of the system and the PP bond order

Open Access June 2, 2014

Hochdruckreaktionen quaternärer Chalkogenide mit Schichtstruktur / High-Pressure Reactions of Quaternary Layered Chalcogenides

N. Berand, H. Haeuseler, K.-J. Range

Page range: 785-789

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Abstract

The layered chalcogenides CoGa 1.7 Ti 0.3 S 4 , CoGa 1.7 V 0.3 , CoGa 1.6 Cr 0.4 S 4 , CoGaInS 4 , MnGa 1.5 Cr 0.5 S 4 , MnGa 1.4 Sc 0.6 S 4 , MnGa 0.8 In 1.2 S 4 , MnIn 2 S 1.6 Se 2.4 and CdIn 2 S 2.1 Se 1.9 have been investigated under high-pressure - high-temperature conditions (p ≤ 60 kbar, T ≤ 1600°C). MnIn 2 S 1.6 Se 2.4 and CdIn 2 S 2.1 ,S 1.9 show a phase transition to spinel-type compounds (a = 11.022(2) and a = 11.059(1) Å, respectively). MnGa 0.8 In 1.2 S 4 forms a high-pressure polymorph with an olivine-type structure (a = 12. 856(3), b = 7.500(3), c = 6.128(2)Å. All other compounds decompose under the conditions applied. The results of a Rietveld structure refinement for the two high-pressure spinels are presented

Open Access June 2, 2014

Ligand Influences on the Supramolecular Chemistry of Simple Gold(I) Complexes: Mononuclear (Isonitrile)gold(I) Complexes

Wolfgang Schneider, Klaus Angermaier, Alexander Sladek, Hubert Schmidbaur

Page range: 790-800

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Abstract

A series of (isonitrile)gold(I) complexes has been synthesized: (MeNC)AuX (X = Cl la, I lc), (t-BuNC)AuBr 2b. (PhNC)AuX (X = Cl 3a. Br 3b. I 3c. SCN 3d), (MesNC)AuCl 4a [mes=mesityl], and (MeOC(O)CH 2 NC)AuX (X = Cl 5a. Br 5b. I 5c. SCN 5d). The chlorides were prepared by the reaction of (Me 2 S)AuCl with equimolar amounts (or with an excess) of the corresponding isonitrile. The bromides, iodides and thiocyanates were obtained from the reaction of (RNC)AuCl with K + X - (X = Br, I, SCN) in the two-phase system H 2 O/CH 2 CI 2 . The molecular and crystal structures of la. 2b. 3a-c, 4a, and 5a-c have been determined by X-ray diffraction methods. In the solid state the molecules are aggregated through short Au-Au contacts into dimers (4a and 5c), chains (la, 2b and 3a-c) or sheets (5a and 5b). The influence of the isonitrile and halide ligands on the type and strength of the intermolecular Au-A u contacts is discussed

Open Access June 2, 2014

Polynuclear Gold Complexes of the Carbodiimide Unit [N=C=N]^2-

W. Schneider, K. Angermaier, H. Schmidbaur

Page range: 801-805

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Abstract

The reaction of N,N′-bis(trimethylsilyl)carbodiimide with equimolar quantities of tris[(triphenylphosphine)gold]oxonium tetrafluoroborate in dichloromethane at -40°C gives high yields of a trinuclear complex {[(Ph 3 P)Au] 2 NCN[Au(PPh 3 )]} + BF 4 - (1). According to variable temperature NMR data the cation is fluxional in solution with a rapid site exchange of the [(Ph 3 P)Au] units, but has an unsymmetrical (N,N,N′) low temperature ground state configuration. A single crystal X-ray diffraction study has shown that in the crystal lattice these cations are associated further into cyclic, hexanuclear dimers through two short head-to-tail Au-Au contacts (auriophilicity). Treatment of complex 1 with one equivalent of [(Ph 3 P)Au] + BF 4 - in tetrahydrofuran affords a tetranuclear complex {[(Ph 3 P)Au] 2 NCN[Au(PPh 3 )] 2 } 2+ 2BF 4 - (2). The ambient temperature NMR spectra of 2 suggest a fluxional, pseudo-symmetrical structure, but at low temperature a set of three 31 P signals (1:2:3 intensity) indicates an aggregation into higher nuclearity species with non-equivalent [Au(PPh 3 )] units

Open Access June 2, 2014

The Stannides EuPdSn and EuPtSn

Rainer Pöttgen

Page range: 806-810

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Abstract

EuPdSn and EuPtSn were prepared from the elements in tantalum tubes at 1070 K and investigated by X-ray diffraction on both powder as well as single crystals. They crystallize with the TiNiSi type structure of space group Pnma and with Z = 4 formula units per cell. Both structures were refined from single-crystal diffractometer data: a = 751.24(9), b = 469.15(6), c = 804.31(9) pm, V = 0.2835(1) nm 3 for EuPdSn, and a = 753.38(7), b = 467.72(4), c = 793.08(7) pm, V = 0.2795(1) nnr for EuPtSn. The structures consist of three-dimensional [PdSn] and [PtSn] polyanionic networks in which the europium atoms are embedded. The crystal chemistry of these stannides is briefly discussed

Open Access June 2, 2014

Hochdrucksynthese und Kristallstruktur von Nd₄Au₂O₉ und Gd₄Au₂O₉ / High Pressure Synthesis and Crystal Structure of Nd₄Au₂O₉ and Gd₄Au₂O₉

Claudia Steiner, Martina Andratschke, Klaus-Jürgen Range

Page range: 811-816

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Abstract

Single crystals of Nd 4 Au 2 O 9 and Gd 4 Au 2 O 9 have been prepared by oxidizing mixtures of gold metal and Nd 2 O 3 or Gd 2 O 3 , rsp., with KO 2 under high-pressure high-temperature conditions (40 kbar, 1200°C) in a modified Belt-type apparatus. The X-ray structure analyses have been carried out on twinned crystals. The compounds crystallize in the orthorhombic space group Pbcn (Nd 4 Au,O 9 : a = 11.938(7) ,b = 6.126(2),c = 11.928(3) A ,Z = 4,1 = 0.0443; Gd 4 Au 2 O 9 : a = 11.922(2), 6 = 6.1242(7), c = 11.917(2) A, Z = 4. R1 =0.0232). The title compounds are isostructural with La 4 Au 2 O 9 . Their structure comprises isolated square-planar AuO 4 groups, stacked along [010] to form a columnar structure. The Au-Au distance along the columnar direction is 3.10 Å. Structural relations to Bi 2 CuO 4 und (Nd, Pr) 2 AuO 5 are discussed

Open Access June 2, 2014

Zwei monokline Kupfer-Oxovanadate des Magnesiums mit geordneter Metallverteilung: m-Mg₂CuV₂O₈ und MgCu₂V₂O₈. Ein Beitrag zur Dimorphie von Mg₂CuV₂O₈ / Two Monoclinic Copper Oxovanadates of Magnesium Showing Ordered Metal Distribution: m-Mg₂CuV₂O₈ and MgCu₂V₂O₈. A Contribution on Dimorphism of Mg₂CuV₂O₈

O. Schrandt, Hk. Müller-Buschbaum

Page range: 817-821

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Abstract

Single crystals of ra-Mg 2 CuV 2 O 8 (I) and MgCu 2 V 2 O 8 (II) have been prepared by solid state reactions. The orange (I) and dark red (II) crystals show monoclinic symmetry, space group C 5 2h -P2 1 /c, (I): a = 6.167(3), b = 8.172(5), c = 6.400(8) Å, β = 116.22(3)°, Z = 2; (II): a = 6.453(1), b = 8.342(2), c = 11.517(2)Å,β 90.44(2), Z = 4. Both compounds show ordered metal distributions and vanadium in tetrahedral coordination by oxygen. (I) is characterized by elongated CuO 6 octahedra and (II) by trigonal CuO 5 bipyramids. m-Mg 2 CuV 2 O 8 is the low temperature form of the formerly investigated orthorhombic o-Mg 2 CuV 2 O 8 . Calculations of the Coulomb parts of the lattice energy of the two crystal forms are discussed

Open Access June 2, 2014

Zur Kristallchemie eines Natrium-Cadmium-Oxoiridats: Na₃Cd₂IrO₆ / On the Crystal Chemistry of a Sodium Cadmium Oxoiridate: Na₃Cd₂IrO₆

S. Frenzen, Hk. Müller-Buschbaum

Page range: 822-825

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Abstract

Single crystals of Na 3 Cd 2 IrO 6 have been prepared by crystallization from melts in closed silver tubes. The crystal structure was investigated by X-ray techniques. Na 3 Cd 2 IrO 6 , crystallizes with monoclinic symmetry, space group C 3 2h -C2/m; a = 5.663(2), b = 9.783(3), c = 5.689(2) Å, β = 109.95(2)°, Z = 2. It is isotypic to M + 5 A 7+ O 6 (M = Li, Na; A = Re, Os) and shows relations to the sodium chloride structure in spite of an ordered distribution of Na + , Cd 2+ and Ir 5+

Open Access June 2, 2014

Die Kristallstrukturen der Eisen- und Cobalt-Hexacyanokomplexe Rb₂LiM(CN)₆ und Rb₂NaM(CN)₆ / The Crystal Structures of the Iron- and Cobalt-Hexacyanocomplexes Rb₂LiM(CN)₆ and Rb₂NaM(CN)₆

Stefan Peschel, Werner Paulus, Dietrich Babel

Page range: 826-831

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Abstract

The crystal structures of four isotypic cyano complexes, belonging to the monoclinic type of cryolite (P2 1 /n, Z = 2), were determined by single crystal X-ray methods and in one case also by neutron diffraction: Rb 2 LiFe(CN) 6 (a = 717.3, b = 748.0, c = 1030.2 pm, β = 90.24°; Fe - C = 193.6, C - N = 114.5, Li - N = 227.0 pm), Rb,NaFe(CN) 6 (a = 724.5, b = 772.5, c = 1055.2 pm, β = 90.39°; Fe - C = 193.9, C - N = 114.2, Na - N = 250.4 pm), Rb,LiCo(CN) 6 (a = 715.5, b = 741.2, c = 1025.0 pm, β = 90.14°; Co - C = 189.6, C - N = 114.3, Li - N = 226.9 pm), Rb 2 NaCo(CN) 6 (a = 722.5, b = 766.3, c = 1049.2 pm, β = 90.33°; Co - C = 189.9 (188.8), C - N = 113.4 (7/5.5), Na - N = 250.6 (249.6 pm). The irregular [RbN 8 l coordination polyhedra exhibit average distances close to Rb - N = 336 pm. Details are discussed and the results compared with those of related compounds

Open Access June 2, 2014

Synthesis, Infrared and X-Ray Studies of Diphenyltellurium(IV) Nitrosocarbamylcyanmethanides. X-Ray Evidence for Stability of a Tritelluroxane Fragment -Ph₂Te-O-Ph₂Te-O-Ph₂Te-

Konstantin V. Domasevitch, Victor V. Skopenko, Eduard B. Rusanov

Page range: 832-837

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Abstract

Diphenyltellurium(IV) derivatives of the types Ph 2 Te{ACO} 2 (1), Ph 4 Te 2 O{ACO} 2 (2) and Ph 6 Te 3 O 2 {ACO} (3) (ACO = nitrosocarbamylcyanmethanide - ONC(CN)C(O)NH 2 ) have been prepared. The IR spectroscopic data reveal that the ambidentate ligands are coordinated to the tellurium(IV) atom in a monodentate manner via the nitroso oxygen atom. The crystal and molecular structure of 3 has been determined from X-ray diffraction data (triclinic, space group P1̅ with a = 12.382(2), 6=13.100(2), c = 14.944(3) Å, a = 87.74( 1), β = 85.04(2), 7 = 66.29( 1)°, V = 2211.0 A , Z = 2, R = 0.040). The structure is made up of unsymmetric molecules, in which the tellurium atoms are linked by oxo bridges to form chains Te-O-Te-O-Te (d(Te-O) ca. 1.94-2.09 A). The Te-0 (nitroso group) bond lengths are in the range 2.33 - 2.36 Å

Open Access June 2, 2014

Zur Reaktivität des Germaethens Me₂Ge=C(SiMe₃)₂: Mechanistische Aspekte der Diels-Aider- und En-Reaktionen [1] / On the Reactivity of Germaethene Me₂Ge=C (SiMe₃)₂: Mechanistic Aspects of Diels Alder and Ene Reactions [1]

Nils Wiberg, Susanne Wagner

Page range: 838-850

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Abstract

Diels-Alder and ene reactions of germaethene Me 2 Ge=C(SiMe 3 ) 2 (2) with butadienes respectively, take place regioselectively, as well as stereoselectively. They are accelerated by an increasing tendency of substituents in butadiene or propene to donate electrons (e.g. 2-methylbutadiene > butadiene; 2-methylpropene > propene), and retarded by an increasing bulkyness of substituents in 1,4- or 1,3-positions (e.g. 1-methylbutadiene > 2-methylbutadiene; 1-vinylpropene > propene). It is concluded from these studies that Diels-Alder and ene reactions of 2 occur - like those of Me 2 Si=C(SiMe 3 ) 2 (1) or of ethenes >C=C< - in a concerted way and are HOMO diene -LUMO dienophile and HOMO ene -LUMO enophile controlled. Thus 2 and 1 behave as carbon analogues. With regard to a specific diene or ene (e.g. anthracene; toluene), 2 is the better dienophile or enophile than 1 or ethenes. With a fixed diene/ene mixture (e.g. butadiene/propene), 2 acts as the better dienophile, while 1 is the better enophile. These results can be explained by the π/π*- energy difference and the double bond polarity decreasing in the direction 1 > 2. Only cis-piperylene gives a [2+2] cycloadduct with 2. besides two [4+2] cycloadducts, and an ene reaction product

Open Access June 2, 2014

1,1-Organoboration of Trimethyl-l-propynyltin Using Diorganoboryl-Substituted Ferrocenes

Bernd Wrackmeyer, Udo Dörfler, Wolfgang Milius, Max Herberhold

Page range: 851-858

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Abstract

The reactions of various diorganoborylferrocenes, Fc -BR 2 [1, R = Me (a), Et (b), i Pr (c), t Bu (d), Ph (f), R 2 B = 9-borabicyclo[3.3.1]nonyl (e)] and 1,1′-bis(9-borabicyclo[3.3.1]nonyl)- ferrocene (2) with trimethyl-l-propynyltin (3) were studied, and the products of the 1,1- organoboration were characterized as the alkenyltin compounds 4 -6 by 1 H, 11 B, 13 C and 119 Sn NMR. In the cases of 1a - 1d and If, there is competition between the transfer of a ferrocenyl group and the other organyl groups R from boron to carbon, whereas in the case of the 9-borabicyclo[3.3.1]nonane derivatives 1e and 2, the enlargement of the bicyclic system takes place selectively (compounds 4e and 6). The molecular structure of the product 6, obtained from the reaction between the 1,1′-diborylated ferrocene 2 and two equivalents of 3, was determined by single crystal X-ray analysis (space group P2 1 /c monoclinic; Z = 4, a = 958.3(2), b = 1610.4(3), c = 2405.3(5) pm and β = 90.33(3)°)

Open Access June 2, 2014

Synthesis of Pentaalkyl-6-bromo-2,3,4,5-tetracarba-nido-hexaboranes(6)

Bernd Wrackmeyer, Alexandra Glöckle

Page range: 859-864

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Abstract

Peralkylated 2,3,4,5-tetracarba-mdo-hexaboranes(6) 1 react with boron tribromide, BBr 3 , via selective exchange of the alkyl substituent in 6-position to give the corresponding new 6- bromo derivatives 2 in quantitative yield. The 6-iodo derivatives 2(1) can be prepared in the same way using BI 3 . Treatment of the carbaboranes 2 with Li Et 3 BH leads to the 1,2,3,4,5- pentaalkyl-2,3,4,5-tetracarba-inido-hexaboranes(6) 3. 1,3,4,6-Tetraethyl-2,3,4,5-tetracarbaw do-hexaborane(6) 4 reacts with BBr 3 via degradation of the carbaborane cage to give EtBBr 2 , and (Z)-1,4-bis [bis(dibromoboryl)]-3-hexene 5. A new bis(diethylboryl)-substituted dialkenyl(bromo)borane 8 was prepared, but attem pts failed to convert it into a 1-bromo- or 6-bromo-mdo-C 4 B 2 -carbaborane. Treatment of 1,1-dialkyl-3-diethylboryl-4-ethylstannoles 9 with a large excess of BBr 3 also affords 5, whereas 6-bromo-l,3,4-triethyl-2,3,4.5-tetracarbamdo- hexaborane(6) 11 was isolated in low yield (<5%) from the reaction between 9 and BBr 3 (slight excess)

Open Access June 2, 2014

Eine unerwartete Synthese des Triphenyphosphazenium-chlorids, [(C₆H₅)₃PNH₂]⁺CI_– und eine Neubestimmung seiner Kristallstruktur / An Unaspected Synthesis of Triphenylphosphazenium Chloride, [(C₆H₅)₃PNH2]⁺Cl^– , and a Redeterm ination of its Crystal Structure

H. Vogt, A. Fischer, P. G. Jones

Page range: 865-868

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Abstract

Triphenylphosphazenium chloride has been prepared by the reaction of triphenylphosphine with trimethylsilylazide in impure, wet dichloromethane. Yields are improved as stoichiometric quantities of water are added. Colourless crystals are obtained by recrystallization from the same solvent. The crystals are triclinic, space group P1̅, Z=2, a = 894,6(3), b - 979,8(3), c = 1142,9(4) pm, α = 107,27(3), β = 93,70(3), y = 92,97(3)°. In the solid state the compound exists as [(C 6 H 5 ) 3 PNH 2 ] + cations, and Cl - anions. Dimeric units are formed by H-bonding. The crystal structure contains one molecule CH 2 Cl 2 per one molecule (C 6 H 5 ) 3 PNH 2 Cl. The cation has a slightly irregular tetrahedral geometry around the P-atom with a relatively short P-N bond

Open Access June 2, 2014

Komplexe eines vierzehngliedrigen Tetraazadibenzo-Makrocyclus. Strukturen des freien und zweifach protonierten Liganden und seiner Nickel(II)-, Kupfer(II)-, Zink(II)- und Palladium(II)-Komplexe / Complexes of a 14-Membered N₄ Dibenzo Macrocycle. Crystal Structures of the Free and Diprotonated Ligand and of its Nickel(II), Copper(II), Zink(II) and Palladium (II) Complexes

Ralf Feldhaus, Jens Köppe, Rainer Mattes

Page range: 869-878

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Abstract

The synthesis and structural characterisation of complexes of the 14-membered macrocyclic trans-N 4 dibenzo ligand 5,6,7,8,9,14.15,16,17,18-decahydrodibenzo[e,l][1,4, 8,11]-tetraazacyclotetradecine (L 2 ) is described. The crystal structures of six compounds were determined by single crystal X-ray diffraction. The free ligand L 2 has a saddle-shaped structure with short intramolecular hydrogen bonds. The N-N distances are 289 pm. The diprotonated species [H 2 L 2 ] 2+ has a different conformation due to intra- and intermolecular hydrogen bonds. The ligand is folded along an N-N axis in c/s-[Ni(L 2 )(H 2 O) 2 ] 2+ , but displays a saddleshaped structure in the Cu(II), Zn(II) and Pd(II) complexes with a more or less planar arrangement of the four N donor atoms. The metal atoms are incorporated within the macrocyclic cavity in [Cu(L 2 )(CF 3 SO 3 )] + and [Pd(L 2 )] 2+ . The metal-to-nitrogen bond lengths herein are rather small. Zn(II) is five-coordinate in [Zn(L 2 )(Cl)] + . The coordination polyhedron is intermediate between a trigonal bipyramid and a square pyramid. In all complexes the metalto- ligand distances originating at the nitrogen atoms in β-position (with respect to the aromatic ring) are significantly shorter then the donor bonds of the ‘anilinic’ N atoms

Open Access June 2, 2014

Preparation and Structure of Poly(gold)telluronium Salts

Klaus Angermaier, Hubert Schmidbaur

Page range: 879-882

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Abstract

Tris[(triphenylphosphine)gold(I)]telluronium tetrafluoroborate (1) was prepared from the corresponding oxonium salt and bis(t-butyldimethylsilyl)tellurium in dichloromethane at -78°C. The product forms yellow crystals, thermally stable to 125°C. It was identified by standard analytical and spectroscopic techniques, including a single crystal X-ray diffraction study. In the crystal lattice, the cations form tellurium-capped triangles of gold, which are associated into dimers through short intermolecular Au -Au contacts, resembling those in the corresponding sulfur and selenium compounds. - The reaction of (t-BuMe 2 Si) 2 Te with four equivalents of [(Ph3P)Au]BF4 in tetrahydrofuran at -78°C gives a tetranuclear compound, {[(Ph 3 P)Au] 4 Te} 2+ 2 BF 4 - (2) which differs from 1 in its analytical and spectroscopic data. Its structure could not be determined, but it is assumed that the dications have a square pyramidal geometry

Open Access June 2, 2014

Synthese und Kristallstruktur von Pb₂LnAl₃O₈ (Ln = Eu, Gd) / Synthesis and Crystal Structure of Pb₂LnAl₃O₈ (Ln = Eu, Gd)

J.-P. Werner, Hk. Müller-Buschbaum

Page range: 883-887

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Abstract

Single Crystals of Pb 2 LnAl 3 O 8 (Ln = Eu, Gd) have been prepared by flux techniques. The compounds crystallize with cubic symmetry, space group Oh-Pn3̅m, a(Eu) = 9.4578(5), a(Gd) = 9.4448(7) Å, Z = 4. The crystal structure is characterized by heterocubane units of the type Pb 4 O 4 and hexagonal bipyramids of oxygen around the rare earth ions. These components form a network made of macro polyhedra of the type Pb 4 O 4 - LnO 6 - Pb 4 O 4

Open Access June 2, 2014

Preparation of an Aminoxyl Analog of the Anticancer Agent Miltefosine

George Sosnovsky, Jan Lukszo, Robert C. Brasch

Page range: 888-890

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Abstract

The synthesis and a few properties of hexadecyl 2-[N,N-dimethyl-N-(2,2,6.6-tetramethyll- oxyl-piperidin-4-yl)ammonio] ethyl phosphate are described. This compound is a spin labeled analog of the antineoplastic drug hexadecylphosphocholine (Miltefosine)

Open Access June 2, 2014

Synthesis of Methyl 6-Deoxy-6-diphenylphosphino-α-D-glucopyranoside: Temperature-Dependence of the Primary O-Tosyl Cleavage Mode

Wilhelm V. Dahlhoff, Karin Radkowski

Page range: 891-896

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Abstract

Methyl α-D-glucopyranoside is converted to methyl 6-p-toluenesulfonyl-2,3,4-tris-O-trimethylsilyl- α-D-glucopyranoside 2 and then reacted with lithium diphenylphosphide in THF. When the reaction is carried out at room tem perature and below, S-O cleavage dominates giving methyl 2,3,4-tris-O-trimethylsilyl-α-D-glucopyranoside 3 , whereas at 60°C in THF or at 35°C in diethyl ether, C-O cleavage occurs yielding the title carbohydrate-phosphine 4 in good yield after deprotection

Open Access June 2, 2014

Triterpene Glycosides from Polygala klotzschii

Hans Ch. Krebs, Petra Sollinger

Page range: 897-900

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Abstract

Polygala klotzschii is a toxic plant growing in Brazil. From the methanolic extract of its leaves, two triterpene glycosides could be isolated. Their structures have been determined by spectroscopic means as well as through degradation reactions and by preparing the alditolacetates. The glycosides were identified as 28-0-[β-D-glucofuranosyl(1-2)-β-D-xylopyranosyl(1-4)-α-L-rhamnopyranosyl(1-4)-[α-D-xylopyranosyl(1-3)]-β-D-xylopyranosyl]-3-0-β-D-glucopyranosyl- medicagenate (1) and 28-0-[α-L-rhamnopyranosyl( 1 -4)-a-L-rhamnopyranosyl( 1 -4)-[/3-Dxylofuranosyl( 1-2)-β-D-xylopyranosyl( l-3)]-β-D-xylopyranosyl]-3-0-β-D-glucopyranosyl- 16α-hydroxymedicagenate (2) respectively

Open Access June 2, 2014

Synthese und Redoxverhalten schwefelsubstituierter Naphthochinone-1,4 / Synthesis and Redox Behaviour of Sulfur Substituted Naphthoquinones-1,4

Torsten Knieß, Roland Mayer

Page range: 901-904

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Abstract

Chloro substituted naphthoquinones-1,4 1 react with di-Na-4,5-dithio-1,3-dithiol-2-thiones 2 and other dithiolates to give new sulfur containing heterocyclic quinones 3 and 4 as possible preliminary states to synthesize tetrathiafulvalenes. The reaction of 1 with di-Li-2,2- bis(methylthio)-1,1-ethylendithiol 8 yields the appropriate bis-(methylthio)methylen substituted naphthoquinones 9. The redox behaviour of the new compounds was investigated by cyclic voltammetry

Open Access June 2, 2014

Neue Pnictide mit modifizierten AIB₂-Strukturen / New Pnictides with Modified AIB₂-Type Structures

Dirk Johrendt, Reiner Miericke, Albrecht Mewis

Page range: 905-906

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Abstract

Nine new compounds AMX with A: Ca, Sr, Ba, M: Pd, Au and X:P, As were prepared by heating mixtures of the elements and investigated by Xray methods. They crystallize in modified AIB 2 - type structures, for the present examples in the ZrBeSi- and SrPtSb-types, with an ordered distribution of the atoms

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 51 Issue 6

Issue of Zeitschrift für Naturforschung B

Abstract

Polynuclear Gold(I) Complexes of Mercaptocarboxylic Acids

Abstract

Phosphonio-substituierte 1,3-Diphosphanaph thaline aus der a,o-Kondensation von Phosphonium-benzyliden / Phosphonio-Substituted 1,3-Diphosphanaphthalenes from the α.o-Condensation of Phosphonium-benzylides

Abstract

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Hochdruckreaktionen quaternärer Chalkogenide mit Schichtstruktur / High-Pressure Reactions of Quaternary Layered Chalcogenides

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Ligand Influences on the Supramolecular Chemistry of Simple Gold(I) Complexes: Mononuclear (Isonitrile)gold(I) Complexes

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Polynuclear Gold Complexes of the Carbodiimide Unit [N=C=N]2-

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The Stannides EuPdSn and EuPtSn

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Hochdrucksynthese und Kristallstruktur von Nd4Au2O9 und Gd4Au2O9 / High Pressure Synthesis and Crystal Structure of Nd4Au2O9 and Gd4Au2O9

Abstract

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Zur Kristallchemie eines Natrium-Cadmium-Oxoiridats: Na3Cd2IrO6 / On the Crystal Chemistry of a Sodium Cadmium Oxoiridate: Na3Cd2IrO6

Abstract

Die Kristallstrukturen der Eisen- und Cobalt-Hexacyanokomplexe Rb2LiM(CN)6 und Rb2NaM(CN)6 / The Crystal Structures of the Iron- and Cobalt-Hexacyanocomplexes Rb2LiM(CN)6 and Rb2NaM(CN)6

Abstract

Synthesis, Infrared and X-Ray Studies of Diphenyltellurium(IV) Nitrosocarbamylcyanmethanides. X-Ray Evidence for Stability of a Tritelluroxane Fragment -Ph2Te-O-Ph2Te-O-Ph2Te-

Abstract

Zur Reaktivität des Germaethens Me2Ge=C(SiMe3)2: Mechanistische Aspekte der Diels-Aider- und En-Reaktionen [1] / On the Reactivity of Germaethene Me2Ge=C (SiMe3)2: Mechanistic Aspects of Diels Alder and Ene Reactions [1]

Abstract

1,1-Organoboration of Trimethyl-l-propynyltin Using Diorganoboryl-Substituted Ferrocenes

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Synthesis of Pentaalkyl-6-bromo-2,3,4,5-tetracarba-nido-hexaboranes(6)

Abstract

Eine unerwartete Synthese des Triphenyphosphazenium-chlorids, [(C6H5)3PNH2]+CI– und eine Neubestimmung seiner Kristallstruktur / An Unaspected Synthesis of Triphenylphosphazenium Chloride, [(C6H5)3PNH2]+Cl– , and a Redeterm ination of its Crystal Structure

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Preparation and Structure of Poly(gold)telluronium Salts

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Synthese und Kristallstruktur von Pb2LnAl3O8 (Ln = Eu, Gd) / Synthesis and Crystal Structure of Pb2LnAl3O8 (Ln = Eu, Gd)

Abstract

Preparation of an Aminoxyl Analog of the Anticancer Agent Miltefosine

Abstract

Synthesis of Methyl 6-Deoxy-6-diphenylphosphino-α-D-glucopyranoside: Temperature-Dependence of the Primary O-Tosyl Cleavage Mode

Abstract

Triterpene Glycosides from Polygala klotzschii

Abstract

Synthese und Redoxverhalten schwefelsubstituierter Naphthochinone-1,4 / Synthesis and Redox Behaviour of Sulfur Substituted Naphthoquinones-1,4

Abstract

Neue Pnictide mit modifizierten AIB2-Strukturen / New Pnictides with Modified AIB2-Type Structures

Abstract

Polynuclear Gold Complexes of the Carbodiimide Unit [N=C=N]^2-

Hochdrucksynthese und Kristallstruktur von Nd₄Au₂O₉ und Gd₄Au₂O₉ / High Pressure Synthesis and Crystal Structure of Nd₄Au₂O₉ and Gd₄Au₂O₉

Zur Kristallchemie eines Natrium-Cadmium-Oxoiridats: Na₃Cd₂IrO₆ / On the Crystal Chemistry of a Sodium Cadmium Oxoiridate: Na₃Cd₂IrO₆

Die Kristallstrukturen der Eisen- und Cobalt-Hexacyanokomplexe Rb₂LiM(CN)₆ und Rb₂NaM(CN)₆ / The Crystal Structures of the Iron- and Cobalt-Hexacyanocomplexes Rb₂LiM(CN)₆ and Rb₂NaM(CN)₆

Synthesis, Infrared and X-Ray Studies of Diphenyltellurium(IV) Nitrosocarbamylcyanmethanides. X-Ray Evidence for Stability of a Tritelluroxane Fragment -Ph₂Te-O-Ph₂Te-O-Ph₂Te-

Zur Reaktivität des Germaethens Me₂Ge=C(SiMe₃)₂: Mechanistische Aspekte der Diels-Aider- und En-Reaktionen [1] / On the Reactivity of Germaethene Me₂Ge=C (SiMe₃)₂: Mechanistic Aspects of Diels Alder and Ene Reactions [1]

Eine unerwartete Synthese des Triphenyphosphazenium-chlorids, [(C₆H₅)₃PNH₂]⁺CI_– und eine Neubestimmung seiner Kristallstruktur / An Unaspected Synthesis of Triphenylphosphazenium Chloride, [(C₆H₅)₃PNH2]⁺Cl^– , and a Redeterm ination of its Crystal Structure

Synthese und Kristallstruktur von Pb₂LnAl₃O₈ (Ln = Eu, Gd) / Synthesis and Crystal Structure of Pb₂LnAl₃O₈ (Ln = Eu, Gd)

Neue Pnictide mit modifizierten AIB₂-Strukturen / New Pnictides with Modified AIB₂-Type Structures