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Facet   section ZfN Section B:Volume 041  [X]
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1986 (263)
201Author    H.-D Hausen, W. Schwarz, G. Rajca, J. WeidleinRequires cookie*
 Title    Die Spektren und Kristallstrukturen der Addukte Cl5Sb [N(i-C3H7)CN(/-C3H7)] und Cl4Sn -2 [N(i-C3H7)CN(/-C3H7)]  
 Abstract    Spectra and Crystal Structures of the Adducts C l5Sb • [N(/-C3H 7)C N (i-C3H 7)] and C l4Sn • 2 [N(/-C3H 7)CN(/-C3H 7)j X-Ray, Vibrational Data, Diisopropylcarbodiimide Adducts of SbCl5, SnCl4 Thecarbodiimide adducts Cl5Sb<-(—N (R) = C = N R)(1) and Cl4S n ^ (-N (R) = C = N R) 2(2)(R = /-C3H 7) have been prepared by the reaction o f R —N = C —N — R with SbCl5 in a 1:1 and with SnCl4 in a 2:1 molar ratio, respectively. The vibrational spectra (IR and Raman) of both compounds have been regarded and assigned to the skeleton modes. The X-ray structure determination shows the orthorhombic space group Pna2, with 4 formula units per unit cell for 1. Adduct 2 has a trans-configuration and crystallizes in the triclinic space group P 1 with only one molecule per unit cell. 
  Reference    Z. Naturforsch. 41b, 1223—1229 (1986); eingegangen am 20. Juni 1986 
  Published    1986 
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 Identifier    ZNB-1986-41b-1223 
 Volume    41 
202Author    Michael Zettlitzer, Heindirk Tom Dieck, Lutz StampRequires cookie*
 Title    Reactions of N-Silated Endiamines, I Transition Metal Complexes of l,3-Diaza-2-sila-4-cyclopentenes  
 Abstract    1,3-Diaza-2-sila-4-cyclopentenes 1 (D ISC), which are electron-rich and easily oxidizable ole­ fins, form strongly coloured, but poorly soluble 1:1 adducts with cuprous halides, while silver trifluoromethylsulfonate oxidizes 1. Much more soluble and again strongly coloured complexes of stoichiometry LPdX2, (L)15PdX2 and L 2PdX2 are formed from 1 and palladium halides. The well-crystallizing adduct (PdCl-,-L)o 3a was chosen for an X-ray structure analysis (monoclinic, space group P 21c; a = 10.215(3), b = 14.681(3), c -23.642(5) A , ß = 101.31(2)°; Z = 8 ; R = 0.054), which revealed an almost planar D ISC ligand in an oblique ?z2(C=C)-coordination relative to the 7r-plane. Structural data and rather peculiar spectroscopic properties encourage a comparison of 3a with complexes, in which an electron-rich olefin is split to give a bis(carbene) ligand system. The electronic reasons for the splitting of electron-rich olefins at d8 metals are discussed under symmetry considerations. 
  Reference    Z. Naturforsch. 41b, 1230—1238 (1986); eingegangen am 12. Februar/9. Juni 1986 
  Published    1986 
  Keywords    Endiamines, Palladium Complexes, X-Ray, Electron-Rich Olefins, Carbene-Type Complexes 
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 Identifier    ZNB-1986-41b-1230 
 Volume    41 
203Author    Joseph Grobe, Norbert KrummenRequires cookie*
 Title    Alternativ-Liganden XX [1]  
 Abstract    Neue Komplexe M(CO)3L mit Tripodliganden MeGe(OCH2PMe2)3 und MeSi(OCH2PMe2M C H 2CH2PMe2)3_* (M = Cr, Mo, W; a: = 0-2) Alternative Ligands X X [1] Novel Complexes M (C O)3L with Tripod Ligands M e G e (O C H 2PM e2)3 and M e S i(O C H 2PM e2)v(C H 2C H 2PM e2)3_ v (M = Cr, M o, W ; x = 0-2) Tripod Phosphane Ligands,/ öc-M(CO)3L Complexes (M = Cr, Mo, W), 'H N M R Spectra, 3IP N M R Spectra Tripod ligands M eG e(O C H 2PMe2)3 (1) and M eSi(O CH 2PMe2)A (C H 2C H 2PMe2)w (x = 0-2) (4—6) have been prepared by reacting MeGeCl, and MeSiClvV i3_v (j: = 1,2), respectively, with Me2PCH 2O H in the presence of a tertiary amine (NEt, or NMe3), in case of the resulting vinyl-silane derivatives M eSi(OCH 2PMe2)vV i3^. (x — 2: 2; x = 1: 3) and MeSiVi, followed by the photochemical addition of Me:PH to the vinyl groups. Replacement of the cyclohepta-triene ligand in M (C O)3CHT compounds (M = Cr, Mo, W) yields the new complexes fac-M (C O)3[MeGe(OCH2PMe2)3] (7-9) and/ac-M(CO)3[MeSi(OCH2PMe2),(C H 2C H 2PMe2)3_,] (10—18). The ligand properties of 1 and 4—6 have been studied by determining the effects of coordination on the spectroscopic data (vco, lH. 3IP N M R). 
  Reference    Z. Naturforsch. 41b, 1239—1246 (1986); eingegangen am 24. Juni 1986 
  Published    1986 
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 Identifier    ZNB-1986-41b-1239 
 Volume    41 
204Author    Hans-Jochen Meder, Wolfgang BeckRequires cookie*
 Title    Metallkomplexe mit biologisch wichtigen Liganden, XLII [1] Carbonylmetallkomplexe mit Anionen von mehrfunktionellen «-Aminosäuren Metal Complexes with Biologically Important Ligands, X L II [1] Carbonyl Metal Complexes with Anions of Polyfunctional a-Amino Acids  
 Abstract    Carbonyl Complexes of Chromium, Molybdenum. Tungsten, Anions of Functional a-Amino Acids as Ligands A series of carbonyl metal complexes with anions of functional «-amino acids has been pre­ pared: [M(CO),(L-histidinate)]' (M = Cr, Mo, W), M(CO),(L-histidinate) (M = Mn, Re), [Re(CO)3(NO)(L-histidinate)] + PF6-, M (C O)2(//3-allyl)(L-histidinate) (M = Mo, W), M o(C O)2(NO)(L-histidinate), [M o(CO)(NO)(^3-methalIyl)(L-histidinate)]PF6, M o(C O)2(/73-methallyl)(L-histidineOMe)Cl, [M(CO)3(cysteinate)]2~ (M = Mo, W), [Mo(CO)3(glyglyO)(H2C))]", [Re(CO)3(L-ornithinate)(CH3CN)] and [Re(CO)3(L-lysinate)]. The IR and N M R data of the new complexes are reported. 
  Reference    Z. Naturforsch. 41b, 1247—1254 (1986); eingegangen am 30. Mai 1986 
  Published    1986 
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 Identifier    ZNB-1986-41b-1247 
 Volume    41 
205Author    Joanne Mcgeachie, LindsayA. SummersRequires cookie*
 Title    Formation of Triradical Trications from Hexaquaternary Salts Derived from 4,4'-Bipyridine  
 Abstract    The syntheses of the hexaquaternary salts l,l'-bis-[2-(r-methyl-[4,4'-bipyridinium]-l-yl)-ethyl]-4,4'-bipyridinium hexaperchlorate and l,l'-bis-[3-(l'-methyl-[4,4'-bipyridinium]-l-yl)-propyl]-4,4'-bipyridinium hexaperchlorate are reported. The salts are reduced in aqueous solu­ tion to triradical trications at a potential (E0) of —0.24 V. We recently reported the preparation of tetra-quaternary salts derived from 4,4'-bipyridine of the 
  Reference    Z. Naturforsch. 41b, 1255—1259 (1986); received April 17 1986 
  Published    1986 
  Keywords    4, 4'-Bipyridinium Hexaquaternary Salts, Reduction Potentials, Triradical Trications 
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 Identifier    ZNB-1986-41b-1255 
 Volume    41 
206Author    Hubert Martin, R. Udolf, HerrmannRequires cookie*
 Title    Oxidation of Imines by Selenium Dioxide  
 Abstract    The oxidation of imines containing a a-methylene group by selenium dioxide is investigated. The products are shown to be a-imino carbonyl compounds by spectroscopic methods. The reactivity of various imines is discussed. 
  Reference    Z. Naturforsch. 41b, 1260—1264 (1986); received May 25 1986 
  Published    1986 
  Keywords    Selenium Dioxide, Imines, a-Imino Carbonyl Compounds 
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 Identifier    ZNB-1986-41b-1260 
 Volume    41 
207Author    Heinrich Volz, Michael Hassler, Hermann SchäfferRequires cookie*
 Title    meso-Substituierte Porphyrine, 4 [1] raeso-Substituted Porphyrins, 4 [1]  
 Abstract    meso-Tetraarylporphyrins, raeso-Tetraarylporphinatoiron(III) Complexes, me50-Tetramesitylporphinatoiron(III)methoxide, raeso-Tetraarylporphinatoiron(III)hydroxides, /<-Oxo-bis(meso-tetraarylporphinatoiron(III)) 2-Pyrryl-(3,5-dimethylphenyl)-carbinol, 2-pyrryl-(3,5-di-f-butyl-phenyl)-carbinol and 2-pyrryl-mesityl-carbinol are cyclised in acidic medium to the corresponding meso-tetraarylporphyrins. The raeso-tetraarylporphyrins are transfered to the iron complexes. The reactions of the iron-porphyrins with O H e and H ,C O e are studied and the products of these reactions are character­ ised. 
  Reference    Z. Naturforsch. 41b, 1265—1272 (1986); eingegangen am 4. April 1986 
  Published    1986 
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 Identifier    ZNB-1986-41b-1265 
 Volume    41 
208Author    Franz Daliacker, Hans-Joachim Schieuter, Petra SchneiderRequires cookie*
 Title    Darstellung und Reaktionen von 1,3-Benzdioxol-biscarbaldehyden Ein Beitrag zur Strukturaufklärung des Nepenthons A Synthesis and Reactions of 1,3-Benzodioxoledicarboxaldehydes A Contribution to the Structure Elucidation of Nepenthone-A  
 Abstract    1,3-B enzdioxole-5,6-dicarboxaldehyde, l,3-B enzdioxole-4,5-dicarboxaldehyde, 4,7-D im ethoxy-l,3-b en zod ioxole-5,6-d icarb oxaldehyde We describe the preparation o f l,3-Benzodioxole-5,6-dicarboxaldehyde (ld) and 1,3-Benz-dioxole-4,5-dicarboxaldehyde (3h). Under especially mild conditions also the synthesis o f 4,7-D im eth oxy-l,3-benzodioxole-5,6-dicarboxald eh yde (4g) can be achieved. Its reaction with H ydroxyacetone leads to quinone 9a, which after m ethylation can be iden­ tified with the dim ethylether o f N epenth one-A . 
  Reference    Z. Naturforsch. 41b, 1273—1280 (1986); eingegangen am 5. Mai 1986 
  Published    1986 
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 Identifier    ZNB-1986-41b-1273 
 Volume    41 
209Author    Hans Albert, UlrikeM. Ayr3, Günther SchmidtbergbRequires cookie*
 Title    Über die Wellenlängen-Abhängigkeit der Photo-Eliminierung des Biphenyl-Systems aus cis-Bis(phenyl)platin(II)-Verbindungen  
 Abstract    Bis(phenyl)platinum (II), Photochem istry, W avelength D epend en ce Excitation o f the com pounds c/5 -{Pt[P(/j-C4 H 9)3 ]2 (4 -X C 6 H 4)2} with radiation o f the wavelengths 287.5 and 312.0 nm resulted in the reductive elim ination of the substituted biphenyls 4-X C 6 H 4 —C6 H4 X -(4) (X = CF3, C H 3, C (C H 3)3, O C H 3), whereas they are photostable towards irradiation of 253.5 nm. It is dem onstrated that the elim ination is a regiospecific pericyclic reac­ tion at platinum; no free radicals are involved. 
  Reference    Z. Naturforsch. 41b, 1281 (1986); eingegangen am 16. April 1986 
  Published    1986 
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 Identifier    ZNB-1986-41b-1281 
 Volume    41 
210Author    Angelo Albim, Silvia SpretiRequires cookie*
 Title    Photooxidation of Methylbenzenes and Methylnaphthalenes Sensitized by Cyanoanthracenes  
 Abstract    Photooxidation, M ethylbenzenes, M ethylnaphthalenes, Cyanoanthracenes 9-Cyanoanthracene, 9,10-dicyanoanthracene and 3 ,7 ,9 ,10-tetracyanoanthracene photosensitize the oxidation in acetonitrile o f tolu en e, durene. hexam ethylbenzene, 1 -methyl-and 2 -methyl-naphthalene to the corresponding aldehydes, with low yield of the alcohols and, in the case of hexam ethylbenzene, o f tetram ethylphthalide. In benzene, only hexam ethylbenzene reacts through a different pathway involving singlet oxygen. Comparison with fluorescence quenching data and experim ents in the presence o f good donors, halides or radical traps, as well as the effect o f solvents and o f oxygen concentration show that the reaction involves electron transfer from the m ethylaromatic to the singlet excited state o f the sensitizer, follow ed by proton transfer to C A T or 0 2t yielding benzyl radicals, which react with oxygen or can be trapped. 
  Reference    Z. Naturforsch. 41b, 1286 (1986); received April 7 1986 
  Published    1986 
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 Identifier    ZNB-1986-41b-1286 
 Volume    41 
211Author    George Sosnovsky, N. Uma, M. Aheswara, R. Ao, Jan LukszoRequires cookie*
 Title    Synthesis of Water Soluble Spin Labeled Glucose Derivatives as Potential NMR Contrast Enhancing Agents  
 Abstract    o f W isconsin-M ilw aukee, M ilwaukee, W isconsin 53201, U SA and R obert C. Brasch Contrast A gents for N M R Imaging, Spin Labeled G lucose D erivatives, Spin Labeled Carbohydrates, Nitroxyls Synthetic m ethodologies for the preparation of nitroxyl labeled derivatives of D -(+)-glucose, a -D -(+)-m ethylglycoside, 2-am ino-2-deoxy-D -(+)-glucose, and D -(+)-glucuronic acid are pre­ sented. The spin labels in these com pounds are attached variably at the 1, 2, 3, and 6 positions of the glucose framework. T hese new com pounds, being water soluble and producing marked en ­ hancem ent o f spin-lattice (T ,) and spin-spin (T2) proton relaxation in deionized water and human plasma have potential utility as contrast altering pharmaceuticals for magnetic resonance imaging and as spin probes in biom olecular research. These spin labeled carbohydrates may dem onstrate in vivo biodistribution characteristics reflecting tissue-specific differences in glucose m etabolism . 
  Reference    Z. Naturforsch. 41b, 1293—1305 (1986); received March 13 1986 
  Published    1986 
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 Identifier    ZNB-1986-41b-1293 
 Volume    41 
212Author    M. Anfred RegitzRequires cookie*
 Title    Tetra-terf-butylprismane durch Dewarbenzol-Isomerisierung  
 Abstract    The kinetically stabilized cyclobutadiene 2 undergoes [4+2]-cycloaddition reaction at elevated temperature with the acetylenecarboxylate 3 to yield the regioisom eric dewarbenzenes 5 and 6. They are transformed into the prismanes 7 and 8 by a photochem ical intramolecular [2+2]-cycloaddition process. Under thermal conditions (150 °C) this isom erization reaction is reversible (7— >5, 8— *6). 
  Reference    Z. Naturforsch. 41b, 1306 (1986); eingegangen am 16. Mai 1986 
  Published    1986 
  Keywords    [4+2]-C ycloaddition, Cyclobutadiene Chemistry, D ew arbenzenes, Prismanes 
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 Identifier    ZNB-1986-41b-1306 
 Volume    41 
213Author    Berthold Buchholz, A. Ndreas, O. Nistschenko, H. Elm, Ut StammRequires cookie*
 Title    Reactions with Aziridines, 37 [1] N,N'-Substituted 1,1-Dimethylethylenediamines by Highly Regioselective Ring Opening of Activated 2,2-Dimethylaziridines through Aliphatic Amines  
 Abstract    2,2-D im ethylethylenediam ines, A ctivated 2,2-D im ethylaziridine, N ucleophilic Ring O pening, Steric Hindrance, A m ines 
  Reference    Z. Naturforsch. 41b, 1311 (1986); received M ay 30 1986 
  Published    1986 
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 Identifier    ZNB-1986-41b-1311 
 Volume    41 
214Author    M. Anfred, M. Utter+, Ltm Ann, ThomasV. OrherrRequires cookie*
 Title    The Construction of New Proteins* II. Design, Synthesis and Conformational Studies of Folding Units with /ta/J-Topology*  
  Reference    Z. Naturforsch. 41b, 1315 (1986); received April 18 1986 
  Published    1986 
  Keywords    Artificial Proteins, ß a ß -Folding U n its, Conform ational Studies, Liquid-Phase Peptide Synthesis, Tertiary Structure 
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 Identifier    ZNB-1986-41b-1315 
 Volume    41 
215Author    Hans Möhrle, Heinz DwuletzkiRequires cookie*
 Title    Ring-Ketten-Isomerie substituierter Tetrahydropyridinderivate Ring Chain Isomerism of Substituted Tetrahydropyridines  
 Abstract    Ring Chain Isomerism, Tetrahydropyridines, d-A m in oketones, Cyclic Iminium Salts The reactions of d-brom oketones 1 with amines lead to cyclic enam ines 6 or secondary d-am inoketones 3 depending on the nature o f the amine used. A m ino substituents which increase the nucleophilicity forces the course o f the reaction towards cyclisation to 6 , which in turn yields the corresponding iminium salts 5. This pathway can be suppressed by large substituents leading to the formation of am monium salts 4. <3-Anilinoketones 3 represent borderline cases because they cyclise only in acidic media. 
  Reference    Z. Naturforsch. 41b, 1323—1327 (1986); eingegangen am 22. Mai 1986 
  Published    1986 
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 Identifier    ZNB-1986-41b-1323 
 Volume    41 
216Author    Armin Weiss, Eugen Riegler, Christian RoblRequires cookie*
 Title    Transition Metal Squarates, U On the Structure of Cubic (MC40 4-2H 20 ) r C H jC 0 0 H H 20 (M = Zn2+, Ni2+) [1]  
 Abstract    The isotypic com pounds (M C 40 4'2 H:0) r C H 3C 0 0 H H 20 (M = Z n2+, N i2+) crystallize in the cubic space group Pn3n. The 3-dim ensional framework structure contains cavities, which may be filled with C H ,C O O H • H 20 . The metal ions are coordinated almost octahedrally by two water m olecules and four oxygen atom s of four C40 42 dianions. Thus the squarate dianions act as fourfold m onodentate ligands. Strong hydrogen bonding betw een H 20 and C40 42 has to be assum ed. 
  Reference    Z. Naturforsch. 41b, 1329—1332 (1986); received May 28/July 15 1986 
  Published    1986 
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 Identifier    ZNB-1986-41b-1329 
 Volume    41 
217Author    Armin Weiss, Eugen Riegler, Christian RoblRequires cookie*
 Title    Ubergangsmetallquadratate, III Über die trikline Käfigstruktur des (MC40 4*2 H20 ) 3* CH3COOH* H20 (M = Zn2+, Mn2+) [1] Transition Metal Squarates, III On the Triclinic Cage Structure of (MC40 4 * 2 H20 ) 3-CH3COOH ■ H20 (M = Zn2+, Mn2+) [1]  
 Abstract    The isostructural com pounds (M C40 4 -2 H 20)3 • C H ,C O O H • H :0 (M = Zn2+, Mn:+) crystallize in the triclinic space group P I , if grown in solution of high ionic strength. The structural features are similar to those in the cubic phase. Correspondingly C H ,C O O H • H ;0 can be trapped in cage­ like cavities, formed by the 3-dim ensional framework o f M2t" and C40 42 . The metal ions are coordinated in a distorted octahedral fashion. The squarate dianions act as four-fold m onodentate ligands. 
  Reference    Z. Naturforsch. 41b, 1333 (1986); eingegangen am 4. Juni/15. Juli 1986 
  Published    1986 
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 Identifier    ZNB-1986-41b-1333 
 Volume    41 
218Author    Christian Robl, Armin WeissRequires cookie*
 Title    Komplexe mit substituierten 2,5-Dihydroxy-/?-benzochinonen: ZnC6( N 0 2)20 4 * 2 H20 Complexes with Substituted 2,5-Dihydroxy-p-benzochinones: ZnC6(N 0 2)20 4 ■ 2 ILO  
 Abstract    Zinc Nitranilate. Preparation, Hydrogen Bonding ZnC 6(N 0 2)20 4 • 2 H 20 was grown in aqueous silicagel. It crystallizes m onoclinically (space group I2/c). Z n2+ has C N 6 . It is surrounded in a distorted octahedral fashion by 2 water m olecules in m -p o sitio n and 4 oxygen atoms o f the bis-chelating [C6(N 0 2)20 4]: ~ ions. Thereby infinite corrugated chains are formed consisting of Z n2+ and the nitranilate dianions. T hese chains are interlinked by hydrogen bonds between H 20 and the N 0 2 groups. The N O : groups are twisted against the ring plane. The bond lengths in the dianion are typical of com pletely delocalized .Tr-electrons. 
  Reference    Z. Naturforsch. 41b, 1337—1340 (1986); eingegangen am 27. Juli 1986 
  Published    1986 
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 Identifier    ZNB-1986-41b-1337 
 Volume    41 
219Author    Christian Robl, Armin WeissRequires cookie*
 Title    Synthesis and Crystal Structure of CuC40 4*2 H20  
 Abstract    C opper Squarate, Chain Structure The m onoclinic compound CuC40 4-2 H ;0 (space group P 2 t/c) was prepared from aqueous 
  Reference    Z. Naturforsch. 41b, 1341—1345 (1986); received May 28/July 15 1986 
  Published    1986 
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 Identifier    ZNB-1986-41b-1341 
 Volume    41 
220Author    Gerhard Thiele, Joachim Großmann, AlbertWolfgang PürzerRequires cookie*
 Title    Kubische Cyanomercurate NR4MHg(CN)4 (R = Et, Pr; M = Li, Na, K, Cu) mit Alumosilikatstruktur On Cubic Cyanomercurates NR4MHg(CN)4 (R = Et, Pr; M = Li, Na, K, Cu) with Alumosilicate Type Structure  
 Abstract    Quaternary Cyanomercurates N R 4"[M H g(C N)4]~ with R = Et, Pr; M = Li, Na, K, Cu, obtained by reactions of N R 4C N . MCN and H g(C N)2 in polar solvents, are dim orphous. The low temperature modifications are tetragonal with a space group 14, the high temperature forms are cubic with the space group F 43m . Reversible phase transitions were studied by DSC, Raman spectroscopy and X-ray diffraction. They are o f first order and of displacive character. The X-ray structure determ inations o f the cubic forms of N E t4M H g(C N)4 with M = Na, Li showed tetra­ hedral M (N C)4-and H g(C N)4-groups connected by linear M —N C —Hg bridges to give three-dimensional frameworks o f a cristobalite type structure and with cavaties, in which the N E t4+ cations are located. 
  Reference    Z. Naturforsch. 41b, 1346—1350 (1986); eingegangen am 16. Juli 1986 
  Published    1986 
  Keywords    Cyanom ercurates, Crystal Structure, Cristobalit Type Structure, Cyano Com plexes, Mercury Com pounds 
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 Identifier    ZNB-1986-41b-1346 
 Volume    41 
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