Published by De Gruyter

Volume 39 Issue 8

Issue of Zeitschrift für Naturforschung B

Contents
Journal Overview

Open Access June 2, 2014

Metallacycloalkane, VIII η⁵-Cjclopentadienyl-η²-methylencyclopropan-Cobaltkomplexe und deren Umwandlung in η⁴-Butadien-Cobaltkomplexe über Cobaltacyclopentane/ Metallacycloalkanes. VIII η⁵ -Cyelopentadienyl-η²-Methylenecyclopropane Complexes of Cobalt and their Transformation into η⁴-Butadiene Complexes via Cobaltacyclopentanes

Paul Binger, Tony Ronald Martin, Reinhard Benn, Anna Rufińska, Gerhard Schroth

Page range: 993-1000

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Abstract

The η 5 -cyclopentadienyl-bis(η 2 -methylenecyclopropane)cobalt complexes 5 and 6 were prepared by reaction of CpCo-bis(ethylene) (4) with methylenecyclopropane (1) and 2,2,3,3-tetramethylm ethylenecyclopropane (2), which on heating isomerise via non-isolable cobaltacyclopentanes and 4-m ethylene-cobaltacyclohexanes to give the CpCo-1,3-butadiene derivatives 10, 11 and 12. The same type of isomerisation can be observed by reacting CpCo(triphenylphosphane)( acrylonitrile) with 1 leading to the CpCo-1,3-butadiene derivative (15). With diphenylm ethylenecyclopropane (3) only a CpCo-monomethylenecyclopropane complex is formed, which isomerises immediately to give CpCo(1,1-diphenyl-1,3-butadiene) (13) and in minor amounts the fluxional binuclear cobalt complex 14. All new cobalt complexes were fully characterised by means o f high resolution NM R spectroscopy.

Open Access June 2, 2014

Katalytische Synthese von Hydridmagnesiumchlorid aus Magnesium, Wasserstoff und Magnesiumchlorid/ Catalytic Synthesis of Hydridomagnesium Chloride from Magnesium, Hydrogen and Magnesium Chloride

Borislav Bogdanović, Manfred Schwickardi

Page range: 1001-1003

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Abstract

THF solutions of hydridomagnesium chloride (HMgCl, 1a) can be prepared in nearly quantitative yields by hydrogenation of magnesium in THF solutions of magnesium chloride at 0 °C in the presence of a CrCl 3 -Mg anthracene catalyst. Concentration of saturated HMgCl solutions, or hydrogenation of magnesium under the above mentioned conditions in MgCl 2 -THF suspensions, lead to the formation of THF solutions of species having the approximate com position HMgCl · MgH 2 or 2 HMgCl · MgH 2 .

Open Access June 2, 2014

Organoboron-Monosaccharides, XIII β-D-Mannofuranosides: Highly Stereoselective Syntheses and NMR Characterization

Wilhelm Volker Dahlhoff, Angelika Geisheimer, Gerhard Schroth, Richard Mynott

Page range: 1004-1010

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Abstract

Stoichiometric reactions of 2,3:5,6-di-O-ethylboranediyl-α-D -mannofuranosyl bromide (1) with O -nucleophiles at room temperature give β-D-mannofuranosides with excellent stereoselectivities. The labile glycosides obtained are deboronated in quantitative yields and then converted to their tetra-O -acetates. The products are characterized by NMR spectroscopy.

Open Access June 2, 2014

Über die katalytische Umwandlung von Olefinen, VIII „Nacktes“ Nickel als Katalysator bei der Umalkylierung von Aluminiumtrialkylen mit α-Olefinen/ The Catalytic Conversion of Olefins, VIII „Naked“-Nickel as a Catalyst for the Transalkylation of Aluminium Trialkyls with α-Olefins

Karl Fischer, Klaus Jonas, Alfred Mollbach, Günther Wilke

Page range: 1011-1021

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Abstract

Nickel(0)-olefin complexes such as tris(ethylene)nickel(0) (4), tris(bicycloheptene)nickel(0) (6 ), all-transcyclododecatriene)nickel(0) (26), tris(stilbene)nickel(0) (27) and bis(cyclooctadiene) nickel(0) (23) are highly active homogeneous catalysts for the transalkylation of aluminium trialkyls with α-olefins. After com pletion of the reaction the nickel(O) can be rem oved in the form of Ni(CO) 4 by reaction with CO. Characteristic for the catalytic reaction is the formation of olefin-nickel-π-bonds and Ni -C -Al multi-centre-bonds. The mechanism o f the reaction is discussed with the help of m odels.

Open Access June 2, 2014

1,4-Dithia-2,6-diaza-3,5-diborinane: Ein neues B–N–S-Ringsystem/ 1.4-Dithia-2.6-diaza-3,5-diborinanes: A Novel B – N –S-Ringsystem

Carl Habben, Anton Meller

Page range: 1022-1026

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Abstract

The novel 1,4-dithia-2,6-diaza-3,5-diborinane ring system results from the reaction of 3,5- dialkyl- (or di-sec.amino-) substituted 1,2,4-trithia-3,5-diborolanes with 1.3-disubstituted sulfurdiimides by replacement of the disulfane bridge. Upon treatment with azomethines, 3,5-dibromo- 1.2.4-trithia-3,5-diborolane gives 3,5-dibromo-1,2-dithia-4-aza-5-diborolidines by substitution of the sulfur atom in position 4. 1 H , 11 B , 13 C, 29 Si NMR and mass spectra are reported and discussed.

Open Access June 2, 2014

Diboran(4)-Moleküle mit Boratomen unterschiedlicher Koordinationszahl/ Diborane(4) Molecules with Boron Atoms with Different Coordination Number

Wolfgang Haubold, Johann Hrebicek, Gisela Sawitzki

Page range: 1027-1031

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Abstract

Molecules with directly bonded boron atoms with different coordination numbers (10, 11, 12 and 13) can be prepared from suitable bifunctional bases like 6, 7, 8 or 9 and C12B - BC12 (1) in an appropriate solvent at high dilution. Properties and spectroscopic data - including 1 J( 11 B- 11 B) - are described. The molecular structure of 10 was investigated by means of an X-ray structure analysis.

Open Access June 2, 2014

Nickel(0)-katalysierte Synthese von Iminen aus Isocyanaten und Aldehyden/ Nickel(0) Catalysed Synthesis of Imines from Isocyanates and Aldehydes

Heinz Hoberg, Klaus Sümmermann

Page range: 1032-1036

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Abstract

The influence of different ligands upon the nickel(0)-catalysed formation of imines from isocyanates and aldehydes is reported. Carbonyl-free nickel(0) systems are found to be more active and provide a simple synthesis of imines. The catalysis proceeds via a five-membered metallacycle, which has been isolated and characterized.

Open Access June 2, 2014

Organoborierung von Alkinylstannanen, XIV Organoborierung von Bis(alkinyl)stannanen: Mechanismus und Anwendung der ¹¹⁹Sn–NMR-Spektroskopie/ Organoboration of Alkynylstannanes, XIV Organoboration of Bis(alkynyl)stannanes: Mechanism and Application of ¹¹⁹Sn NMR Spectroscopy

Susanna Kerschl, Bernd Wrackmeyer

Page range: 1037-1041

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Abstract

Dimethylbis(phenylethynyl)stannane (1) reacts with trialkylboranes, BR 3 (2), to give bis(alkenyl stannanes (5) (R = C 2 H 5 ), 1-bora-4-stanna-2,5-cyclohexadienes (6 ) (R = C 2 H 5 , C 3 H 7 i ), 1- stanna-2,4-cyclopentadienes (7) (R = C 2 H 5 ) and l-stanna-3-cyclopentenes (8 ) (R = CH 3 , C 2 H 5 ). 13 C and 119 Sn NMR data prove the structure of the reaction products (5 to 8 ). 119 Sn NMR is useful (i) for following the course of the reaction (mechanism!) and (ii) for quantitative analysis of the product distribution. Deorganoboration reactions play an important role in the formation of the various heterocyclic systems.

Open Access June 2, 2014

1,1-EMborierung von 1-Trimethylsilylalkinen/ 1.1-Diboration of 1-Trimethylsilylalkines

Hartmut Klusik, Christine Pues, Armin Berndt

Page range: 1042-1045

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Abstract

1,2-Di-terr-butyl-l,2-dichlorodiborane(4) (1) and l,2-dichloro-1,2-bis(dimethylamino)- diborane(4) (2) add to 1-trimethylsilylalkines 3 a -3d to yield 1,1-bis(rm-butylchloroboryl)- alkenes (4) and 1, 1-bis(chlorodimethylaminoboryl)alkenes (5), respectively, while reaction of 1 with acetylene, trimethylsilylacetylene, 2-butine and 3-hexine leads to 1,2-bis(tert-butylchloroboryl) alkenes (7). Compounds 4, 5 and 7 are characterized by MS. 1 H, 13 C and 11 B NMR spectroscopy.

Open Access June 2, 2014

Bis[(η³-allyl)nickel(μ,η⁵-2,3-dihydro-1,3-diborolyl)]nickeI-Tetradecker- Komplexe mit terminalen Allylliganden/ Bis[(η³-allyl)nickel(μ,η⁵-2,3-dihydro-1,3-diborolyl)]nickel Tetradecker Complexes with Terminal Allyl Ligands

Thomas Kuhlmann, Walter Siebert

Page range: 1046-1049

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Abstract

Reactions between bis(allyl)nickel complexes and alkyl derivatives of 2,3-dihydro-1,3-diborole (1a, b) in refluxing toluene or mesitylene yield deeply colored solutions. By distillation and chromatography the first η 3 -allyl tetradecker complexes 8 were obtained in 4 -15% yield. In the violet residues higher molecular species are present, which could not be identified. The red, oily tetradeckers are characterized by NMR and mass spectra; their formation is discussed.

Open Access June 2, 2014

(η²-Alken)organyIruthenium(II)-KompIexe und Ethyleninsertion in Phenyl-Ruthenium-Bindungen/ (η²-A lkene)organylruthenium (II) Complexes and Ethylene Insertion into Phenyl-Ruthenium Bonds

Herbert Lehmkuhl, Jürgen Grundke, Gerhard Schroth, Reinhard Benn

Page range: 1050-1052

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Abstract

The reaction of the alkyl-bis(triphenylphosphine)ruthenium complexes 1-3 with ethylene (50 -150 bar) at 70 -100 °C proceeds by initial phosphine dissociation to give the η 2 -ethylenealkylruthenium compounds 6 -8 . The phenyl-ruthenium complex 4 reacts, under these conditions, by ethylene insertion into the Ph-Ru bond. Subsequent Ru-βH-elimination gives the diastereomeric η 2 -styrene-hydrido-ruthenium compounds 10a and b. At low ethylene pressure (5 - 8 bar), 1 - 3 react mainly by orthometallation of a phosphinehenyl group followed by rapid ethylene insertion into the resulting Ph-Ru bond and Ru-βH-elimination to give the diastereomeric complexes 9a and b.

Open Access June 2, 2014

Topological Effect on MO Energies, IX. On Topologically Related 1,4-Dibora-2,3-diazarine and 1,4-Dibora-2,5-diazarine

loan Motoc, Oskar E. Polansky

Page range: 1053-1057

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Abstract

Minimal STO-NG (N = 3, 4 and 6 ) basis set non-empirical HF SCF MO calculations have been performed for topologically related 1,4-dibora-2,3-diazarine (S) and 1,4-dibora-2,5-diazarine (T). The equilibrium geometries of these S and T isomers have been computed by symmetry-constraint geometry optimizations using the STO-3G basis set. The calculations lead to the prediction that: i) the T isomer is about 48 kJ/mole less stable than the S isomer, and ii) the π -MO energy patterns of the S and T isomers are in complete agreement with the TEMO theorem, while the bonding σ-MO eigenvalues exhibit four inversion points.

Open Access June 2, 2014

Beiträge zur Chemie des Bors, 148. Diamidobor(1+)-Kationen aus Bis(amino)borhalogeniden durch Halogenid-Abspaltung/ Contributions to the Chemistry of Boron, 148.Diamidobor(1+) Cations from Bis(amino)borhalogenides by Halide Abstraction

Heinrich Nöth, Bernhard Rasthofer, Siegfried Weber

Page range: 1058-1068

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Abstract

Bis(amido)boron(1 + ) cations can be generated from bis(amino)-boron halides and an appropriate halide acceptor. The ease of formation of the diethylamido-2.2.6.6-tetramethylpiperidinoboron-( 1 + ) cation 5 from diethylamino-tetramethylpiperidino-boron halides has been studied and found to increase with decreasing strenght of the boron halogen bond. In the case of bis(2.2.6.6- tetramethyl-piperidino)boron fluoride AlCl 3, BCl 3 , BBr 3 and even BF 3 give access to salts of the bis(tetramethylpiperidino)boron-(1+ ) cation. The tetrabromoborate salt 7c reacts with Ag-triflate to yield the corresponding tetratriflatoborate 7g. Similarly. bis(tetramethylpiperidino)boron chloride 8 , obtained from the tetrachloroborate 7b in boiling pyridine, readily gives bis(tetramethylpiperidino) boron(1 + )-tetrachlorometalates. Bis(tetramethylpiperidino)boron(1 + )-triflate is formed by reaction of 8 with AgOSO 2 CF 3 .

Open Access June 2, 2014

1,3,5-Tri-tert-butyl-2,4,6-triisopropyl-3,5-diaza-1-azonia-2,6-dibora- 4-borata[2.2.0]bicyclohexan, der erste Vertreter der Dewarborazine/ 1,3,5-Tri-tert-butyl-2,4,6-triisopropyl-3,5-diaza-1-azonia-2,6-dibora- 4-borata[2.2.0]bicyclohexane, the First Dewar Borazine

Peter Paetzold, Christoph von Plotho, Günter Schmid, Roland Boese

Page range: 1069-1075

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Abstract

The iminoborane iPr-B ≡ N -tBu (1a), metastable at -78 °C, trimerizes to form (iPrBNtBu) 3 (4a) at elevated temperatures. The determination of the molecular and crystal structure reveals 4a to be a Dewar-borazine-type molecule with two short peripheral BN-double-bonds (136 and 138 pm) and an extra-long bridge BN-single-bond (175 pm). The same trimer 4a is formed by addition of la to the diazadiboretidine-type dimer (iPrBNtBu) 2 , prepared independently. The ethyloboration and the azidoboration of la with BEt 3 and Me 3 SiN 3 , respectively, and the cycloaddition of PhN 3 to 1a follow expected patterns.

Open Access June 2, 2014

Tris(phosphan)-Nickel(0)-Ethen-Komplexe (dmpe)(PR₃)Ni(C₂H₄). Molekülstruktur des (dmpe)(PØ₃ )Ni(C₂H₄)/ Tris(phosphane)-nickel(0)-ethene Complexes (dmpe)(PR₃)Ni(C₂H₄). Molecular Structure of (dmpe)(PO₃)Ni(C₂H₄)

Klaus R. Pörschke, Richard Mynott, Carl Krüger, M. J. Romão

Page range: 1076-1081

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Abstract

Synthesis and properties of tris(phosphane)(ethene)nickel(0) complexes (dmpe)(PR 3 )Ni(C 2 H 4 ) (R = CH 3 (4), c-C 6 H 11 (5), and C 6 H 5 (6)) are reported. In solution. 4-6 are thermolabile and undergo ligand exchange reactions affording tetrakis(phosphane)nickel(0 ) and bis(phosphane)- (ethene)nickel(0) complexes. 1 H, 13 C, and 31 P NMR data of 4-6 confirm the tetrahedral geometry around nickel. For 6 , the crystal and molecular structure has been determined by X-ray crystallography.

Open Access June 2, 2014

Azaborolinyl-Komplexe, XV. Bis(η⁵-1,2-azaborolinyI)ruthenium-Sandwichkomplexe – Darstellung und Strukturuntersuchung/ Azaborolinyl Complexes, XV. Bis(η⁵-1,2-azaborolinyl)ruthenium Sandwich Complexes – Synthesis and Structure Investigation

Günter Schmid, Ottmar Boltsch, Dieter Bläser, Roland Boese

Page range: 1082-1087

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Abstract

The synthesis of bis(1-tert-butyl-2 -methyl-η 5 - 1 ,2 -azaborolinyl)ruthenium (1) and bis(2-methyll- trimethylsilyl-η 5 - 1 ,2 -azaborolinyl)ruthenium (2) succeeds when RuCL is reacted with the corresponding 1,2-azaborolinyl lithium compounds in THF at -70 °C. Each of the sandwich complex forms two isomers with a clockwise and an anti-clockwise conformation of the azaborolinyl rings. The anti-clockwise isomer of 1 (1a ) gives colourless crystals which were investigated by singlecrystal X-ray diffraction methods. The molecular structure shows the rings in an eclipsed orientation forming an interplanar angle of 8.6 °. The isomers of 1 as well as of 2 give different 1 H and 11 B NMR signals.

Open Access June 2, 2014

Kristall- und Molekülstruktur von As₂P₂S₇/ Crystal and Molecular Structure of As₂P₂S₇

Wolfgang Hönle, Claus Wibbelmann, Wolfgang Brockner

Page range: 1088-1091

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Abstract

The crystal and molecular structures of As 2 P 2 S 7 has been determined by single crystal X-ray diffraction (space group V 2 1 /c; Z = 4; a = 1174.6(16) pm; b = 823.9(7) pm; c = 1140.1(10) pm; β - 94.43(9)°; R = 0.073. The molecule is isosteric to P 4 S 7 and possesses C 2v symmetry. Mean bond lengths are: d (As-As) = 250.9 pm; d (As-S ) = 225.7 pm; d(P - S) = 208.3 pm and d(P = S) = 193.2 pm. The observed As -As bond length agrees well with spectroscopic results

Open Access June 2, 2014

Reaktionen von Dithiooxamid mit Chlormethylsilanen/ Reactions of Dithiooxamide with Chlormethylsilanes

Herbert W. Roesky, Hartmut Hofmann

Page range: 1092-1094

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Abstract

Reactions of dithiooxamide with chloromethylsilanes are leading to different kinds of products. Depending on the conditions and the reaction pathways N,N′-silylsubstituted dithiooxamides, cyclic dithiooxamides and a dithiooximide can be obtained. All products are sensitive to moisture.

Open Access June 2, 2014

N-Methylcarbamoylphosphate, II. Thermische Zersetzung/ N-Methylcarbamoyl Phosphates, II. Thermal Decomposition

Fritz Seel, Norbert Klein

Page range: 1095-1099

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Abstract

The thermal decomposition of various salts of mono-N-methylcarbamoyl and bis-N-methylcarbamoyl phosphoric acid in aprotic and protic solvents (acetonitrile, trichlorom ethane, alcohols) and in the solid state has been studied in detail. Final products are mono-, di-, poly-, and cyclophosphates, in addition phosphoric acid esters if alcohols are used as solvents; and either sym. dimethylurea or methyl isocyanate and methylamine. The spontaneous decomposition of sparingly soluble N-methyl carbamoyl phosphates in aqueous suspensions to yield slightly soluble diphosphates demonstrates clearly that the reaction of calcium hydrogen phosphate with alkali cyanates via calcium carbam oylphosphate to give calcium diphosphate - which has been considered a prebiotic key reaction - is not a result of a special feature of the structure of the intermediate product.

Open Access June 2, 2014

Darstellung und Schwingungsspektren von Fluoro-Chloro-Osmaten(IV) einschließlich der Stereoisomeren/ Preparation and Vibrational Spectra of Fluoro-Chloro-Osmates(IV) Including Stereoisomers

W. Preetz, D. Ruf, D. Tensfeldt

Page range: 1100-1109

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Abstract

The stepwise replacement of ligands in [OsCl 6 ] 2- by oxidation with BrF 3 generates the mixed complexes [OsF n Cl 6-n ] 2- , n = 1 - 5, of which the species with n = 2,3,4 are cw-configurated. Due to the stronger trans-effect of Cl compared to F on treatment of [OsF 5 Cl] 2- and cis-[OsF 4 Cl 2 ] 2- with Cl - the trans-isomers are formed stereospecifically. The pure fluoro-chloro-osmates(IV) are separated by ion exchange chromatography on diethylaminoethylcellulose. From the pairs of stereoisomers the cis-compounds are always first eluted, whereas the trans-complexes are moving faster in an electric field by 3 to 5% . The vibrational spectra of octahedral mixed ligand complexes are generally discussed according to point groups O h , D 4h , C 4v , C 3v and C 2v . For the fluoro-chloroosmates(IV) all stretching and deformation bands are assigned. They are observed in the characteristic regions; ν(OsF): 625-490 > ν(OsCl): 360-300 > δ (FOsF): 275-210 > δ (FOsCl) > δ (ClOsCl): 190-150 > ν L : < 100 cm -1 .

Open Access June 2, 2014

Die Kristallstruktur von Di-μ-oxo-cis-dioxo-dichloro-bis(2,2′ -bipyridyl)- molybdän(V) (Mo–Mo)-Nitromethansolvat, Mo₂O₄Cl₂(bipy)₂ · CH₃NO₂/ Crystal Structure of Di-μ-oxo-cis-dioxo-dichloro-bis(2,2′-bipyridyl)- molybdenum(V) (Mo–Mo) Nitromethane Solvate, Mo₂O₄Cl₂(bipy)₂ ´ CH₃NO₂

Johannes Beck, Wolfgang Hiller, Eberhard Schweda, Joachim Strähle

Page range: 1110-1113

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Abstract

Mo 2 O 4 Cl 2 (bipy) 2 has been obtained by oxidation of MoCl 4 (bipy) with O 2 in ethanol/H 2 O . The complex crystallizes from CH 3 NO 2 with one solvent molecule per formula unit in the monoclinic space group P 2 1 /n: a = 954.1(2), b = 1925.3(2), c = 1423.2(2) pm, β = 102.48(2)°, Z = 4. The characteristic unit Mo 2 O 4 2+ of the dinuclear complex consists of two terminal oxo ligands in a cisarrangem ent and two bridging oxygen atoms forming a non-planar Mo 2 O 2 ring. A strong Mo -Mo single bond is indicated by a short distance of 256.5 pm. The coordination of both Mo atoms is completed by a Cl atom and a chelating bipyridyl ligand.

Open Access June 2, 2014

ReNF₄ · ReF₅(NCl), ein Nitrido-Nitrenokomplex von Rhenium(VII)/ ReNF₄ · ReF₅(NCl), a Nitrido Nitrene Complex of Rhenium (VII)

Willi Kafitz, Kurt Dehnicke, Eberhard Schweda, Joachim Strähle

Page range: 1114-1117

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Abstract

ReNF 4 · ReF 5 (NCl) is prepared by direct fluorination of ReNCl 4 with fluorine between 80 °C and 130 °C. The red crystals are extremely sensitive to moisture. The complex is characterized by the IR spectrum and by an X-ray structural investigation. ReNF 4 · ReF 5 (NCl) crystallizes orthorhombically in the space group Pnma with 4 formula units per unit cell and with the cell dimensions a = 1440, b = 848, c = 776 pm (419 observed, independent reflexions, R = 13.9%). The complex consists of the molecules ReNF 4 and ReF 5 (NCl), which are linked by a linear asymmetric fluorine bridge. The bridging fluorine atom is in trans-position to the nitrido ligand Re -F - 228 pm) and to the nitreno ligand (Re -F = 159 pm and Re= N - Cl 164 pm) correspond to triple 188 pm). The Re ≡ N bond lengths Re= N bonds.

Open Access June 2, 2014

Strukturverfeinerungen an den Cobalt(II)hexammin-Komplexen [Co(NH₃)₆](BF₄)₂ und [Co(NH₃)₆](PF₆)₂/ Structure Refinements of the Cobalt(II)hexammine Complexes [Co(NH₃)₆](BF₄)₂ and [Co(NH₃)₆](PF₆)₂

S. Kummer, D. Babel

Page range: 1118-1122

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Abstract

Using single crystal X-ray data of the compounds [Co(NH 3 ) 6 ](BF 4 ) 2 (a = 1129.8(1) pm) and [Co(NH 3 ) 6 ](PF 6 ) 2 (a = 1195.9(1) pm) the anti-K 2 PtCl 6 structure, space group Fm3m , was confirmed for both complexes (R ≈ 0.05). Fourier methods revealed essential disorder for the BF 4 - anion only, the fluorine atoms of which remain concentrated, however, within the octants of the subcell opposite to the cobalt atoms. No indication of H bridging is found in the IR spectra. The Co-N bond lengths of 218.3(2) and 218.7(10) pm, resp.. in the cobalt(II)hexammine group are unusual long in both compounds.

Open Access June 2, 2014

Übergangsmetall-substituierte Phosphane, Arsane und Stibane, XLY. Einige Komplexe mit Dreiringstruktur: Aufbau aus Metallo-arsinsulfiden. Öffnung des Metallacyclus mit Phosphordonoren / Transition-Metal Substituted Phosphanes, Arsanes and Stibanes, XLV. Some Complexes with a Three Membered Ring Structure: Formation from Metallo-arsinesulfides. Opening of the Metallacycle with Phosphorus Donors

Michael Luksza, Wolfgang Malisch

Page range: 1123-1128

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Abstract

The interaction of the metallo-arsanes Cp(OC) 2 (L)W - AsR 2 (1a -c) with elemental sulfur or selenium leads to the formation of the metallo-arsinesulfides (selenides) Cp(OC) 2 (L)W -AsR 2 (S,Se) (2a-c), which are converted to the metallacyclic complexes (3a, b) with loss of CO on refluxing in pentane. While the of 3b is cleaved at the W -S bond by (MeO) 3 P to give Cp(OC) 2 [(MeO) 3 P]W -AsMe 2 (S), (4), with an A s-bonded η 1 -thioarsinyl ligand, Me 3 P preferentially cleaves the W -As bond in 3b, d to produce Cp(OC) 2 (Me 3 P)W -S -AsR 2 (5a, b), in which the R 2 As-S-unit is S-coordinated. The spectroscopic data of the new complexes are reported and discussed with respect to the dynamic behaviour of the compounds.

Open Access June 2, 2014

Metallkomplexe mit biologisch wichtigen Liganden, XXXIII. Reaktionen von α-Aminosäuren und α-Aminosäurederivaten mit Gold(III)-chlorid/ Metal Complexes with Biological Important Ligands, XXXIII. Reactions of α-Amino Acids and Derivatives there of with Gold(III) Chloride

Eberhard Ambach, Mano Mohan Singh, Ulrich Nagel, Wolfgang Beck

Page range: 1129-1134

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Abstract

The hydrochlorides of a-aminoacid esters react with Au 2 Cl 6 in thionyl chloride to give the ammonium salts [H 3 NCHRCO 2 R′]+AuCl 4 - (R = H , Me, R′ = H , Me, Et). The X-ray structure of [H 3 NCH(Me)CO 2 Me] + AuCl 4 - has been determined. The reactions of a-aminoacids with Au 2 Cl 6 in SOCl 2 afford mixtures of ammonium tetrachloroaurate(III) salts with a-amino acids, a-amino acid chlorides or a-amino acid anhydrides as amine components. Cysteine esters reduce gold(III) to give the gold(I) compounds [AuSCH 2 CH(N H 2 )CO 2 R] n (R = Me, Et).

Open Access June 2, 2014

³¹P-NMR-spektroskopische Untersuchungen an A₄B₃-Molekülen/ ³¹P NMR Spectroscopical Investigations of A₄B₃ Molecules

R. Blachnik, U . Wickelund, P. Schmitt

Page range: 1135-1138

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Abstract

31 P NMR data of sixteen molecules in the series P 4 S x Se 3-x (x = 0 - 3), PyAs 4-y S 3 , and P y As 4-y Se 3 (y = 0 - 4), resp., are given. All molecules have a common structure, in which a basal ring of three V b-atom s is connected by three chalcogen atom bridges to an apical V b-atom . The dependence of the data on bond angles and electronegativities is discussed. A linear relationship was found betw een chemical shift and an angle increment I=11.3 (∢ endo - 60°) + 5.5 (∢ exo -103°), which describes the bond angle deviations from the reference molecule P 4 S 3 .

Open Access June 2, 2014

Transition Metal Allyls, V. The Preparation and Structure of [NiX(PmenthylR₁R₂)(η³-allyl)] Complexes

H. Brandes, R. Goddard, P. W. Jolly, C. Krüger, R. Mynott, G. Wilke

Page range: 1139-1150

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Abstract

A number of adducts formed by reacting [NiX(η 3 -allyl)] 2 complexes with optically active tert.- phosphines, in which optically active centres are found both at the phosphorus atom and in a substituent, have been isolated and their structures investigated in solution by NMR spectroscopy. The absolute configuration of the phosphine in [NiCl{Pm enthyl(Me)Bu t }(η 3 -C 3 H 5 )] has been determ ined by X-ray crystallography. The relevance of the results to the nickel-catalyzed asymmetric codimerisation of alkenes is discussed.

Open Access June 2, 2014

Notizen: Ba₃Sn₂As₄, eine neue Zintlphase mit Kettenstruktur/ On Ba₃Sn₂As₄, a New Zintl Phase with Chain Structure

Brigitte Eisenmann, Hanna Jordan, Herbert Schäfer

Page range: 1151-1153

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Abstract

The new compound Ba 3 Sn 2 As 4 crystallizes in the monoclinic system (space group: P2 1 /c, No. 14) with the lattice constants a = 806.6(5) pm , b = 1986.1(8) pm , c = 793.1(5) pm , β = 112.3(1)°. The compound is isotypic to Sr 3 Ge 2 As 4 . Octahedral Sn 2 As 6 units are connected by common edges to chains.

Open Access June 2, 2014

Notizen: Reaction Product of Formaldehyd and O-Benzylhydroxylamine: A Schiff Base?

Johannes Respondek

Page range: 1154-1155

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Abstract

200 MHz 1 H and 50 MHz 13 C NMR spectra were recorded from the reaction product of form aldehyd 1 and O -benyzlhydroxylamine 2 for the purpose of its structure elucidation

Open Access June 2, 2014

Notizen: A Dipole Moment Study of Prostaglandins F_1α and F_1β

Giuseppe C. Pappalardo, Antonio Grassi, Marino Nicolini, Henri Lumbroso

Page range: 1156-1158

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Abstract

The experimental electric dipole moments in dioxane solution, together with the calculated dipole moments for some selected conformers, are reported for the two natural prostaglandins F 1α and F 1β . The results obtained are compatible with a hypothesized hairpin structure for these molecules in solution.

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 39 Issue 8

Issue of Zeitschrift für Naturforschung B

Abstract

Katalytische Synthese von Hydridmagnesiumchlorid aus Magnesium, Wasserstoff und Magnesiumchlorid/ Catalytic Synthesis of Hydridomagnesium Chloride from Magnesium, Hydrogen and Magnesium Chloride

Abstract

Organoboron-Monosaccharides, XIII β-D-Mannofuranosides: Highly Stereoselective Syntheses and NMR Characterization

Abstract

Über die katalytische Umwandlung von Olefinen, VIII „Nacktes“ Nickel als Katalysator bei der Umalkylierung von Aluminiumtrialkylen mit α-Olefinen/ The Catalytic Conversion of Olefins, VIII „Naked“-Nickel as a Catalyst for the Transalkylation of Aluminium Trialkyls with α-Olefins

Abstract

1,4-Dithia-2,6-diaza-3,5-diborinane: Ein neues B–N–S-Ringsystem/ 1.4-Dithia-2.6-diaza-3,5-diborinanes: A Novel B – N –S-Ringsystem

Abstract

Diboran(4)-Moleküle mit Boratomen unterschiedlicher Koordinationszahl/ Diborane(4) Molecules with Boron Atoms with Different Coordination Number

Abstract

Nickel(0)-katalysierte Synthese von Iminen aus Isocyanaten und Aldehyden/ Nickel(0) Catalysed Synthesis of Imines from Isocyanates and Aldehydes

Abstract

Organoborierung von Alkinylstannanen, XIV Organoborierung von Bis(alkinyl)stannanen: Mechanismus und Anwendung der 119Sn–NMR-Spektroskopie/ Organoboration of Alkynylstannanes, XIV Organoboration of Bis(alkynyl)stannanes: Mechanism and Application of 119Sn NMR Spectroscopy

Abstract

1,1-EMborierung von 1-Trimethylsilylalkinen/ 1.1-Diboration of 1-Trimethylsilylalkines

Abstract

Bis[(η3-allyl)nickel(μ,η5-2,3-dihydro-1,3-diborolyl)]nickeI-Tetradecker- Komplexe mit terminalen Allylliganden/ Bis[(η3-allyl)nickel(μ,η5-2,3-dihydro-1,3-diborolyl)]nickel Tetradecker Complexes with Terminal Allyl Ligands

Abstract

(η2-Alken)organyIruthenium(II)-KompIexe und Ethyleninsertion in Phenyl-Ruthenium-Bindungen/ (η2-A lkene)organylruthenium (II) Complexes and Ethylene Insertion into Phenyl-Ruthenium Bonds

Abstract

Topological Effect on MO Energies, IX. On Topologically Related 1,4-Dibora-2,3-diazarine and 1,4-Dibora-2,5-diazarine

Abstract

Beiträge zur Chemie des Bors, 148. Diamidobor(1+)-Kationen aus Bis(amino)borhalogeniden durch Halogenid-Abspaltung/ Contributions to the Chemistry of Boron, 148.Diamidobor(1+) Cations from Bis(amino)borhalogenides by Halide Abstraction

Abstract

1,3,5-Tri-tert-butyl-2,4,6-triisopropyl-3,5-diaza-1-azonia-2,6-dibora- 4-borata[2.2.0]bicyclohexan, der erste Vertreter der Dewarborazine/ 1,3,5-Tri-tert-butyl-2,4,6-triisopropyl-3,5-diaza-1-azonia-2,6-dibora- 4-borata[2.2.0]bicyclohexane, the First Dewar Borazine

Abstract

Tris(phosphan)-Nickel(0)-Ethen-Komplexe (dmpe)(PR3)Ni(C2H4). Molekülstruktur des (dmpe)(PØ3 )Ni(C2H4)/ Tris(phosphane)-nickel(0)-ethene Complexes (dmpe)(PR3)Ni(C2H4). Molecular Structure of (dmpe)(PO3)Ni(C2H4)

Abstract

Azaborolinyl-Komplexe, XV. Bis(η5-1,2-azaborolinyI)ruthenium-Sandwichkomplexe – Darstellung und Strukturuntersuchung/ Azaborolinyl Complexes, XV. Bis(η5-1,2-azaborolinyl)ruthenium Sandwich Complexes – Synthesis and Structure Investigation

Abstract

Kristall- und Molekülstruktur von As2P2S7/ Crystal and Molecular Structure of As2P2S7

Abstract

Reaktionen von Dithiooxamid mit Chlormethylsilanen/ Reactions of Dithiooxamide with Chlormethylsilanes

Abstract

N-Methylcarbamoylphosphate, II. Thermische Zersetzung/ N-Methylcarbamoyl Phosphates, II. Thermal Decomposition

Abstract

Darstellung und Schwingungsspektren von Fluoro-Chloro-Osmaten(IV) einschließlich der Stereoisomeren/ Preparation and Vibrational Spectra of Fluoro-Chloro-Osmates(IV) Including Stereoisomers

Abstract

Die Kristallstruktur von Di-μ-oxo-cis-dioxo-dichloro-bis(2,2′ -bipyridyl)- molybdän(V) (Mo–Mo)-Nitromethansolvat, Mo2O4Cl2(bipy)2 · CH3NO2/ Crystal Structure of Di-μ-oxo-cis-dioxo-dichloro-bis(2,2′-bipyridyl)- molybdenum(V) (Mo–Mo) Nitromethane Solvate, Mo2O4Cl2(bipy)2 ´ CH3NO2

Abstract

ReNF4 · ReF5(NCl), ein Nitrido-Nitrenokomplex von Rhenium(VII)/ ReNF4 · ReF5(NCl), a Nitrido Nitrene Complex of Rhenium (VII)

Abstract

Strukturverfeinerungen an den Cobalt(II)hexammin-Komplexen [Co(NH3)6](BF4)2 und [Co(NH3)6](PF6)2/ Structure Refinements of the Cobalt(II)hexammine Complexes [Co(NH3)6](BF4)2 and [Co(NH3)6](PF6)2

Abstract

Abstract

Metallkomplexe mit biologisch wichtigen Liganden, XXXIII. Reaktionen von α-Aminosäuren und α-Aminosäurederivaten mit Gold(III)-chlorid/ Metal Complexes with Biological Important Ligands, XXXIII. Reactions of α-Amino Acids and Derivatives there of with Gold(III) Chloride

Abstract

31P-NMR-spektroskopische Untersuchungen an A4B3-Molekülen/ 31P NMR Spectroscopical Investigations of A4B3 Molecules

Abstract

Transition Metal Allyls, V. The Preparation and Structure of [NiX(PmenthylR1R2)(η3-allyl)] Complexes

Abstract

Notizen: Ba3Sn2As4, eine neue Zintlphase mit Kettenstruktur/ On Ba3Sn2As4, a New Zintl Phase with Chain Structure

Abstract

Notizen: Reaction Product of Formaldehyd and O-Benzylhydroxylamine: A Schiff Base?

Abstract

Notizen: A Dipole Moment Study of Prostaglandins F1α and F1β

Abstract

Organoborierung von Alkinylstannanen, XIV Organoborierung von Bis(alkinyl)stannanen: Mechanismus und Anwendung der ¹¹⁹Sn–NMR-Spektroskopie/ Organoboration of Alkynylstannanes, XIV Organoboration of Bis(alkynyl)stannanes: Mechanism and Application of ¹¹⁹Sn NMR Spectroscopy

Bis[(η³-allyl)nickel(μ,η⁵-2,3-dihydro-1,3-diborolyl)]nickeI-Tetradecker- Komplexe mit terminalen Allylliganden/ Bis[(η³-allyl)nickel(μ,η⁵-2,3-dihydro-1,3-diborolyl)]nickel Tetradecker Complexes with Terminal Allyl Ligands

(η²-Alken)organyIruthenium(II)-KompIexe und Ethyleninsertion in Phenyl-Ruthenium-Bindungen/ (η²-A lkene)organylruthenium (II) Complexes and Ethylene Insertion into Phenyl-Ruthenium Bonds

Tris(phosphan)-Nickel(0)-Ethen-Komplexe (dmpe)(PR₃)Ni(C₂H₄). Molekülstruktur des (dmpe)(PØ₃ )Ni(C₂H₄)/ Tris(phosphane)-nickel(0)-ethene Complexes (dmpe)(PR₃)Ni(C₂H₄). Molecular Structure of (dmpe)(PO₃)Ni(C₂H₄)

Azaborolinyl-Komplexe, XV. Bis(η⁵-1,2-azaborolinyI)ruthenium-Sandwichkomplexe – Darstellung und Strukturuntersuchung/ Azaborolinyl Complexes, XV. Bis(η⁵-1,2-azaborolinyl)ruthenium Sandwich Complexes – Synthesis and Structure Investigation

Kristall- und Molekülstruktur von As₂P₂S₇/ Crystal and Molecular Structure of As₂P₂S₇

ReNF₄ · ReF₅(NCl), ein Nitrido-Nitrenokomplex von Rhenium(VII)/ ReNF₄ · ReF₅(NCl), a Nitrido Nitrene Complex of Rhenium (VII)

Strukturverfeinerungen an den Cobalt(II)hexammin-Komplexen [Co(NH₃)₆](BF₄)₂ und [Co(NH₃)₆](PF₆)₂/ Structure Refinements of the Cobalt(II)hexammine Complexes [Co(NH₃)₆](BF₄)₂ and [Co(NH₃)₆](PF₆)₂

³¹P-NMR-spektroskopische Untersuchungen an A₄B₃-Molekülen/ ³¹P NMR Spectroscopical Investigations of A₄B₃ Molecules

Transition Metal Allyls, V. The Preparation and Structure of [NiX(PmenthylR₁R₂)(η³-allyl)] Complexes

Notizen: Ba₃Sn₂As₄, eine neue Zintlphase mit Kettenstruktur/ On Ba₃Sn₂As₄, a New Zintl Phase with Chain Structure

Notizen: A Dipole Moment Study of Prostaglandins F_1α and F_1β