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1981 (332)
121Author    -), Cyclotetra, Phosphazane, Werner Zeiß, Tino Kuhn, Dieter Lux, Wolfgang Schwarz, Heinz HessRequires cookie*
 Title    (MePNMe)4 Mel und (MePNMe)4 2 Mel, ein Cyclotetra(A 3 .A 3 .A 3 .A 5 -) und ein Cyclotetra(A 3 .A 5 .A 3 .A 5 -phosphazan) (MePNMe)4 * Mel and (MePNMe)4 * 2 Mel, a Cyclotetra  
 Abstract    (2) with three P 111 and one P v , and (3) with two P In and P v atoms are prepared from 1 with methyl iodide. NMR spectra of 2 are compared with those of the recently prepared [1] 4. The crystal structure of 3 shows the molecule to have a crystallographic inversion centre. Thus cis-trans isomerisation must have taken place during the working up procedure. Alkylation has severe consequences on bond distances and bond angles of the cyclotetraphosphazane ring system, in contrast to M(CO)s complexation at the same positions as shown in a similar case recently [8]. 
  Reference    Z. Naturforsch. 36b, 561—565 (1981); eingegangen am 9. Dezember 1980 
  Published    1981 
  Keywords    Cyclotetraphosphazanes, NMR Spectra, Crystal Structure Cyclotetraphosphazanes 
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 Identifier    ZNB-1981-36b-0561 
 Volume    36 
122Author    KlausG. Heumann, Hans-Peter SchieferRequires cookie*
 Title    Calciumisotopenseparation mit Kryptanden als Komplexbildner Separation of Calcium Isotopes with Cryptand Complexes  
 Abstract    The calcium isotope separation in the liquid-liquid extraction system H2O/CHCI3 is investigated using [2.2.1] and [2.2.2] cryptands for complex formation as well as without complexing agent. An extraction procedure is used which allows the transfer of larger amounts of calcium into the CHCI3 phase although the high distribution coefficient favours calcium in the H2O phase. Without complexing agent in the extraction system, enrichment of the lighter calcium isotopes is already evident in the CHCI3 phase which is just the same as when using [2.2.1] cryptand. In the case of [2.2.2] cryptand as a com-plexing agent, the isotope separation is higher. The separation factor is calculated to be a = 1 + e = 1.011 for 40 Ca/ 48 Ca without complexing agent or with [2.2.1] cryptand and a = 1.015 in the system with [2.2.2] cryptand. For 40 Ca/ 44 Ca the e-value is smaller by nearly a factor of two. These separation factors are the highest which are determined in chemical systems for calcium isotopes. 
  Reference    Z. Naturforsch. 36b, 566—570 (1981); eingegangen am 17. Dezember 1980 
  Published    1981 
  Keywords    Isotope Separation, Calcium, Cryptand, Liquid-Liquid Extraction 
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 TEI-XML for    default:Reihe_B/36/ZNB-1981-36b-0566.pdf 
 Identifier    ZNB-1981-36b-0566 
 Volume    36 
123Author    Jochen Ellermann, Leo Mader, Kurt GeibelRequires cookie*
 Title    Chemie polyfunktioneller Liganden, 64 [1] Über Hydridoiridium(III)-Komplexe des N.N-Bis(diphenylphosphino)-p-tolylamiii Chemistry of Polyfunctional Ligands, 64 [1] On Hydridoiridium(III) Complexes of N,N-Bis(diphenylphosphino)-p-tolylamine  
 Abstract    Hydridoiridium(III) Complexes, N,N-Bis(diphenylphosphino)-p-tolylamine, Vibrational Spectra, iH NMR Spectra H2 reacts with [lx{(Ph2P)2N-p-C6H4CH3}2]Cl • 3 C6H6 (1) to give cw-[Ir(H)2{(Ph2P)2N-j9-C6H4CH3}2]Cl • CH2C12 (2a). By reaction of 2a with NaBPh4 cw-[Ir(H)2{(Ph2P)2N-^-C6H4CH3}2]BPh4 (2b) is obtained. Refluxing of 2a in CH2C12 yields «ran5-[Ir(H)2{(Ph2P)2N-p-C6H4CH3}2]Cl • 1/2 CH2C12 (3 a), which undegoes metatheses with NaBPh4 to <rans-[Ir(H)2{(Ph2P)2N-j9-C6H4CH3}2]BPh4 (3b). 3a is also formed by refluxing of 1 in methanol in the presence of oxygen. Oxidative addition of HCl to 1 and reaction with NaBPh4 yields <rans-[Ir(H)(Cl){(Ph2P)2N-p-C6H4CH3}2]BPh4 (4b). The new compounds are characterised by their IR, Raman, 31 P{ 1 H} PFT and 1 H NMR Spectra. 
  Reference    Z. Naturforsch. 36b, 571—577 (1981); eingegangen am 6. Februar 1981 
  Published    1981 
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 Identifier    ZNB-1981-36b-0571 
 Volume    36 
124Author    Ulrich Nagel, Hartmut Menzel, PeterW. Lednor, Wolfgang Beck, Alain Guyot, Michel BartholinRequires cookie*
 Title    Versuche zur Rhodium(I)-katalysierten asymmetrischen Hydrierung von a-Acetamidozimtsäure mit monomeren und polymeren Aminophosphinen Rhodium (I) Catalyzed Asymmetrie Hydrogenation of a-Acetamido Cinnamic Acid with Monomeric and Polymerie Aminophosphines Optically Active l-Phosphino-2-aminopropane, Aminophosphines, Asymmetrie Hydrogenation of a-Acetamido Cinnamic Acid  
 Abstract    An optically active l-phosphino-2-aminopropane, prepared from ephedrine, has been used for the Rh(I) catalyzed asymmetric hydrogenation of a-acetamido cinnamic acid. Optical yields up to 77 percent were obtained. Low stereoselectivity has been found using l,4-bis(diphenylphosphino)-2,5-dibenzylpiperazine and a polystyrene bound bisdiphenyl-phosphine, obtained from phenylalanine. The preparation of optically active piperazines from a-amino acids is reported. 
  Reference    Z. Naturforsch. 36b, 578—584 (1981); eingegangen am 22. Januar 1981 
  Published    1981 
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 Identifier    ZNB-1981-36b-0578 
 Volume    36 
125Author    CliffordW. Fonga, HamishG. GrantRequires cookie*
 Title    Solvent Effects on the Carbon - 13 NMR Chemical Shifts and Rotational Barriers of N,N-Dimethylbenzamide - Solvent Enhanced n Polarization  
 Abstract    The 13 C NMR chemical shifts of N,N-dimethylbenzamide in thirty solvents have been measured at high dilution. The solvent induced chemical shifts (s.i.c.s.) of the carbonyl group carbon atom in twenty three solvents and the thermodynamic barriers to rotation about the C-N bond in eleven solvents are linearly related to the solvent parameter, ET(30). Multi-parametric analysis of the carbonyl s.i.c.s. indicates hydrogen bond donor effects are more important than polar effects. Rotational barriers for N,N-dimethylbenz-amide may be determined by measurement of the 13 C chemical shift of the carbonyl group in a particular solvent. The s.i.c.s. of the aromatic ring carbon atoms may be explained by the polarization of the aromatic ji electron system induced by the solvent enhanced polarization of the dimethylcarboxamido moiety. Hydrogen bonding solvents and polar solvents result in two effective dipoles on the dimethylcarboxamido moiety, which polarize the aromatic n electron system differently. 
  Reference    Z. Naturforsch. 36b, 585—595 (1981); received May 19 1980/January 21 1981 
  Published    1981 
  Keywords    Solvent Effects, 13 C NMR Spectra Rotational Barriers, N, N-Dimethylbenzamide 
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 Identifier    ZNB-1981-36b-0585 
 Volume    36 
126Author    Michael Neumann-Spallart, K. KalyanasundaramRequires cookie*
 Title    On the One and Two-Electron Oxidations of Water-Soluble Zinc Porphyrins in Aqueous Media  
 Abstract    The one and two-electron oxidations of water soluble ionic zinc porphyrins (Zinctetra-methylpyridylporphyrin, ZnTMPyP, Zinc-tetra-p-sulfonato-phenyl-porphyrin, ZnTPPS, and Zinc-tetra-p-carboxy-phenylporphyrin, ZnTPPC) leading to the porphyrin /7-cations and /7-dications have been investigated in water by electrochemical (cyclic voltammetry and controlled potential electrolysis) and chemical methods. The half-wave potentials for the oxidation are shown to be markedly dependent on the charge on the /?-substituents. While the one-electron oxidations for all these porphyrins are reversible, the dication formation leads to labile isoporphyrins as intermediates. 
  Reference    Z. Naturforsch. 36b, 596—600 (1981); received December 1 1980/February 19 1981 
  Published    1981 
  Keywords    Redox Potentials, yr-Cation Radicals, Electrochemistry 
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 Identifier    ZNB-1981-36b-0596 
 Volume    36 
127Author    Alfred StaniendaRequires cookie*
 Title    Energiebilanz einer Reaktion zwischen Radikal-Kation und Radikal-Anion Energy Turnover of a Reaction between Radical Cation and Radical Anion  
 Abstract    AG for the reaction R ,+ + R-~ -> 2 R + AG was calculated according to AG = —(IP-EA) = —A Ei for the reaction in gas phase under ideal conditions. The result was compared with A H in solution measured calorimetrically and the entropy term measured voltammetrically according to AG = A H — TzlS. Both values for AG agreed satisfactorily. From this it was derived that the solvation energies of R ,+ and R— com-pensate mutually. The Coulomb energies have little influence on A G only. 
  Reference    Z. Naturforsch. 36b, 601—608 (1981); eingegangen am 29. Dezember 1980 
  Published    1981 
  Keywords    Radical Ions, Reaction Enthalpy, Ion Solvation, Energy Levels 
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 Identifier    ZNB-1981-36b-0601 
 Volume    36 
128Author    Willy Friedrichsen, Wolf-D Schröer, Ingo Schwarz, Andreas BöttcherRequires cookie*
 Title    Reactions of Mesoionic Five-Membered Heterocycles with o-Quinonoid Compounds, IV [1] Mono-and Tricyclic l,3-Thiazolium-4-olates, l,3-Dithiolylium-4-olates  
 Abstract    o-Quinones, Heterocycles Monocyclic l,3thiazolium-4-olates (10) react with o-quinonoid compounds to give [TT4 + 7i4] cycloadducts (12, 13); tricyclic l,3-thiazolium-4-olates (14, 15) yield compounds (17, 18, 19, 20) which can formally be derived from a ketene tautomer (C). 1,3-Dithiolylium-4-olates are borderline cases; both [JI4+ 7i2] (32) and [n 4 + JZ4] adducts (34) were obtained. A. Einleitung 
  Reference    Z. Naturforsch. 36b, 609—621 (1981); eingegangen am 18. November 1980 
  Published    1981 
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 Identifier    ZNB-1981-36b-0609 
 Volume    36 
129Author    Willy Friedrichsen, Ingo Schwarz, Bernd Epe, Karl-Friedrich HesseRequires cookie*
 Title    Reaktionen mesoionischer Fünfringheterocyclen mit o-chinoiden Verbindungen, V [1, 2] 1.3-Oxazolium-5-olate und 1.3-Thiazolium-5-olate Reactions of Five-Membered Mesoionic Heterocycles with o-Quinonoid Compounds, V [1, 2] l,3-Oxazolium-5-olates and l,3-Thiazohum-5-olates  
 Abstract    o-Quinonoid Compounds, Mesoionic Heterocycles l,3-Oxazolium-5-olates (1) and l,3-thiazolium-5-olates (11) react with o-benzoquinones (3) and a-naphthoquinone to give adducts (4, 5, 6, 15) which can formally be derived from ketone valence tautomers of 1 and 11. 9,10-Phenanthrenequinone and 1 a yield a compound (10) which possibly results from an initially formed [TT4 + JT4] adduct (7) with subsequent loss of CO2. Consistent with this view is a product (14) of the reaction between 9,10-phen-anthrenequinone and 11. The structure of 14 has been determined by X-ray crystallo-graphy. 
  Reference    Z. Naturforsch. 36b, 622—631 (1981); eingegangen am 18. November 1980 
  Published    1981 
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 Identifier    ZNB-1981-36b-0622 
 Volume    36 
130Author    Willy Friedrichsen, Meike Röhe, Tony DebaerdemaekerRequires cookie*
 Title    Cycloadditionen mit o-Benzochinon  
 Abstract    diiminen, VI [1] Reaktionen von Diarylbenzo[c]furanen mit o-Benzochinon-diiminen. Stabile Sessel-und Wannenkonformere in der 5.6.11.12-Tetrahydrodibenzo [b.f] [1.4] diazocinreihe Cycloadditions with o-Benzoquinone-diimines, VI [1] Reactions of l,3-Diarylbenzo[c]furans with o-Benzoquinone-diimines. Stable Chair and Boat Conformers in the 5,6,11,12-Tetrahydrodibenzo[b,f][l,4]diazocin Series Cycloadditions, o-Benzoquinone-diimines N,N'-Diarylsulfonyl-and N,N'-Dibenzoyl-o-benzoquinone-diimines (4) react remarkably easy with l,3-diarylbenzo[c]furans (5) to give [TT4 + ft4] cycloadducts (6). In one case (6a) the chair and boat conformer of this type of adduct could be isolated and the conformations clarified by X-ray crystallography. On heating compounds 6 can rearrange intramolecularly to give 2H-benzimidazoles (7). A. Einleitung 
  Reference    Z. Naturforsch. 36b, 632—643 (1981); eingegangen am 23. Dezember 1980 
  Published    1981 
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 Identifier    ZNB-1981-36b-0632 
 Volume    36 
131Author    M. C. Apella, E. J. BaranRequires cookie*
 Title    On the Crystal Structure of Mixed Phosphate/Sulfate Fluoroapatites  
 Abstract    It is shown that the apatite phases of composi-tion Caio-sNa^PO^e-sfSO^Fa crystallize in a monoclinic unit cell, which is related to those of pure fluoroapatite by doubling the 6-parameter. Some comparisons with related systems are made and a possible explanation for the origin of the small monoclinic distortion is advanced. 
  Reference    Z. Naturforsch. 36b, 644—645 (1981); eingegangen am 26. Februar 1981 
  Published    1981 
  Keywords    Phosphate-Sulfate-Apatites, Crystal Data, Structural Behaviour 
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 Identifier    ZNB-1981-36b-0644_n 
 Volume    36 
132Author    Paul Müller, Weif BrongerRequires cookie*
 Title    Darstellung und Kristallstruktur von Na3FeSe3 Preparation and Crystal Structure of Na3FeSe3  
 Abstract    Crystal Structure, Ternary Selenides Na3FeSe3 can be synthesized by the reaction of sodium carbonate with iron sponge at 1000 K under a stream of hydrogen saturated with selenium or by heating a mixture of sodium hydride and iron sponge with selenium in a glass ampoule with a temperature gradient (700/800 K). X-ray investigation on single crystals revealed the structure of Na3FeSe3, isotypic with that of Na3FeS3. The iron and selenium atoms form isolated [Fe2See]-anions, consisting of two edge-sharing tetrahedra, with which the sodium atoms build a three-dimen-sional array. 
  Reference    Z. Naturforsch. 36b, 646—648 (1981); eingegangen am 23. Februar 1981 
  Published    1981 
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 Identifier    ZNB-1981-36b-0646_n 
 Volume    36 
133Author    Joachim PickardtRequires cookie*
 Title    Die Kristallstruktur von Kalium  
 Abstract    -bis(hexamethylentetramin)-tris-(isothiocyanato)cuprat(II)-dihydrat, K[Cu(C6Hi2N4)2(NCS)3] • 2 H20, einem trigonal-bipyramidalenKupfer(II)-Komplex The Crystal Structure of Potassium-bis(hexamethylenetetramine)-tris-(isothiocy anato) cuprate(II) -dihydrate, K[Cu(C6H12N4)2(NCS)3] • 2 H20, Cupric Complexes, Trigonal Bipyramidal Complexes, Bis(hexamethylenetetramine)-tris-(isothiocyanato)cuprate(II), X-ray 
  Reference    Z. Naturforsch. 36b, 649—650 (1981); eingegangen am 28. Januar 1981 
  Published    1981 
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 Identifier    ZNB-1981-36b-0649_n 
 Volume    36 
134Author    M. Seul, H. Neubacher, W. LohmannRequires cookie*
 Title    Temperature Dependent ESR Studies on Platinum Pyrimidine "Blues": Evidence for a Structural Instability ?  
 Abstract    Frozen samples of aqueous solutions of oxidized Pt 6-methyl-uracil "blue" were studied bv ESR spectroscopy at temperatures T ranging between —196 °C and —10 °C. When T was raised a distinct change in the line pattern was observed at about —35 °C. The resulting type of spectrum is very similar to the ESR spectrum of MAGNUS' Green Salt. The observed effect is suggested to be due to a change of the nature of the system's electronic states possibly indicating a structural rearrangement. 
  Reference    Z. Naturforsch. 36b, 651—653 (1981); received February 12 1981 
  Published    1981 
  Keywords    Platinum Blue, ESR Spectra, Structural Instability, Localized States 
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 Identifier    ZNB-1981-36b-0651_n 
 Volume    36 
135Author    Stanislav Luňák, Josef Vepřek-ŠiškaRequires cookie*
 Title    Could Hydrogen Peroxide Photolysis Occur in the Absence of Transition Metals ?  
 Abstract    Quantum yields of hydrogen peroxide photo-lysis increase with the square root of concentra-tion of added Cu(II). The cupric ions are photo-catalytically active already at trace concentra-tions (10~ 7 M), i.e., at the concentrations present in any real reaction system. Hydrogen peroxide photolysis is completely suppressed on addition of complexing agents such as EDTA. It is believed that no hydrogen peroxide photolysis would occur in complete absence of photo-catalytically active transition metal ions. 
  Reference    Z. Naturforsch. 36b, 654—655 (1981); received February 25 1981 
  Published    1981 
  Keywords    Hydrogen Peroxide, Photocatalysis, Trace Metals 
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 Identifier    ZNB-1981-36b-0654_n 
 Volume    36 
136Author    Dietrich ModerhackRequires cookie*
 Title    On the Hydration of N-Isomeric 5 -Tetrazolecarbaldehy des  
 Abstract    Azole Aldehydes, Hydration, Equilibrium and Rate Constants Of the title aldehydes 1 and 2, the isomers I are more strongly hydrated when kept in dioxan + water or hexadeuterioacetone + deuterium oxide mixtures, respectively. The un-catalysed reaction R-CHO + H20 R-CH(OH)2 proceeds much faster with compounds 1. 
  Reference    Z. Naturforsch. 36b, 656—657 (1981); received February 26 1981 
  Published    1981 
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 Identifier    ZNB-1981-36b-0656_n 
 Volume    36 
137Author    Waldemar Adam, Faris YanyRequires cookie*
 Title    Direct Photochemical cis-trans Isomerization with 185 nm Radiation: A Facile Preparation of cis-Di-tert -buty lethy lene  
 Abstract    On irradiation of £rans-di-ier£-butylethylene at 185 nm in pentane the sterically congested cis-isomer was formed in ca. 40%. This n-n* excitation constitutes a convenient, direct method for the preparation of such usually difficult to prepare olefins. 
  Reference    Z. Naturforsch. 36b, 658 (1981); received February 3 1981 
  Published    1981 
  Keywords    cis-trans Isomerization, 185 nm Photochemistry, n-7i* Excitation, Steric Congestion, Olefin Synthesis 
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 Identifier    ZNB-1981-36b-0658_n 
 Volume    36 
138Author    Heinrich Nöth, Volker Thorn, Frau Professor, DrM. BaudlerRequires cookie*
 Title    Die Stabilisierung von Tris(hydrazino)phosphan durch Komplexbildung The Stabilisation of Tris(hydrazino)phosphane by Complex Formation  
 Abstract    Tris(hydrazino)phosphanes, Stabilisation The solvolysis of (CO)5CrPCl3 with N2H4 or H2N-N(CH3)2 yields (CO)5CrP(NH-NH2)3 and (CO)sCrP[NH-N(CH3)2]3 respectively containing the hitherto unknown and unstable ligands P(NH-NH2)3 and P[NH-N(CH3)2]3. Their constitution is derived from spectro-scopic data. 
  Reference    Z. Naturforsch. 36b, 659—661 (1981); eingegangen am 16. Februar 1981 
  Published    1981 
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 Identifier    ZNB-1981-36b-0659 
 Volume    36 
139Author    Eberhard Schweda, Joachim SträhleRequires cookie*
 Title    Nitrido-azido-Komplexe des Molybdäns(VI) Synthese und Kristallstruktur von MoN(N3)3(NC5H5) Nitrido Azido Complexes of Molybdenum (VI) Synthesis and Crystal Structure of MoN(N3)3(NC5H5)  
 Abstract    The explosive nitrido azido complexes MoN(N3)Cl2 • py and MoN(N3)3py are prepared by the reaction of MoCLi(py)2 with (CH3)3SiN3 in 1,2-dichloroethane. Both compounds hydrolyze quickly in moist air. After separation of the insoluble, black MoN(N3)Cl2 • py from the solution of MoN(N3)3py, the latter can be obtained in form of monoclinic, red crystals of the space group C2/c. Its structure consists of monomeric complexes, wherein the Mo atom has a square pyramidal coordination. The nitrido ligand occupies the apex and forms a strong multiple bond of 163.4 pm to the Mo atom. cr-Bonds of different strength exist between the Mo atom and the basal ligands: M0-N3 — 204.3 pm; Mo-py = 225.8 pm. The a-N atoms of the azido groups are sp 2 hybridized, with their lone pair pointing away from the nitrido ligand. The pyridine ligand forms an angle of 61.6° to the basal plane of the coordination polyhedron. 
  Reference    Z. Naturforsch. 36b, 662—665 (1981); eingegangen am 10. März 1981 
  Published    1981 
  Keywords    Synthesis, Crystal Structure, Molybdenum Nitrido Azido Complexes 
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 Identifier    ZNB-1981-36b-0662 
 Volume    36 
140Author    Requires cookie*
 Title    Perfluormethyl-Element-Liganden, XXV [1] Organozinnverbindungen als Reagenzien, IV: Spaltungsreaktionen der Element-Element-Bindung in Komplexen  
 Abstract    des Typs M(CO)5ER2ER 2 bzw. M(CO)5ER2E R mit Trimethylstannan (R, R =CH3, CF3; E = P, AS; E' =S, Se, Te; M = Cr, Mo) Perfluoromethyl-Element Ligands, XXV [1] Organotin Compounds as Reagents, IV: 
  Reference    Z. Naturforsch. 36b, 666 (1981) 
  Published    1981 
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 Identifier    ZNB-1981-36b-0666 
 Volume    36 
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