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  • 1
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 123 (1990), S. 19-22 
    ISSN: 0009-2940
    Schlagwort(e): Arene complexes / Antimony(III) complexes / Organoantimony compounds / Dihydroanthracene ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Crystals of a 1:2 complex of 9,10-dihydroanthracene and antimony tribromide are obtained from toluene solutions of the components. In the crystal the complex forms corrugated sheets of an inorganic (SbBr3)n coordination polymer, which are cross-linked by antimony coordination to the benzene rings of the dihydroanthracene molecules are also arranged in folded layers. The dihydroanthracene molecules reside on centers of inversion and their carbon skeleton is planar within the limits of the experiment. With contacts from opposite sides of the molecular plane, the dihydroanthracene is η6,(η6)'-coordinated to the Sb(III) centers at distances of 3.25 Å. In a very irregular geometry the coordination sphere of the crystallographically equivalent antimony atoms contains bromine neighbours at different distances. - Antimony trichloride and dihydroanthracene form a complex of ambiguous stoichiometry, while bismuth trichloride again gives a 2;1 complex, the structure of which has not yet been determined.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 2
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 123 (1990), S. 1599-1602 
    ISSN: 0009-2940
    Schlagwort(e): l-Aspartate complexes ; Strontium l-aspartate ; trihydrate ; Barium l-aspartate trihydrate ; Amino acid complexes ; Metal complexation by amino acids ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Strontium and barium l-aspartate are obtained by neutralization of aqueous solutions of l-aspartic acid with strontium or barium hydroxide, respectively. Slow crystallization from hot water affords the crystalline trihydrates, saturated solutions of which show pH values of 11.0 and 10.8 at ambient temperature. - The crystal structure of the two compounds has been determined by single crystal X-ray diffraction. The compounds are isomorphous (orthorhombic, space group P212121), and the structural parameters are very similar as expected from the small differences in the ionic radii of the two metals. - The cations are arranged in double strings parallel to the b axis. The l-aspartate dianions are bridging these double strings by chelating contacts of the two carboxylate groups with the metal atoms of different strings to give layers. While the α-carboxylate groups are only bidentate and associated with one metal atom each, the β-carboxylate oxygen atoms are also each bridging two adjacent metals of the neighbouring string. The three water molecules are all coordinated to the metal atoms, which attain coordination number 9. The amino groups are not engaged in metal coordination, but are part of a system of hydrogen bonds cross-linking the layers.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 3
    ISSN: 0009-2940
    Schlagwort(e): Michaelis-Arbuzov reaction ; Nickel complexes with trimethylphosphite and dimethylphosphito ligands ; Bis(dimethylphosphito)rhodium as chelating ligand ; Organometallic diphenylborane derivative ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Complexes Containing Metallabis(dialky1phosphito) Units, VI1. - Synthesis and Complex-Forming Properties of the Organometallic Chelating Ligand {C5Me5RhI[P(0)(OMe)2]2}-The dinuclear complexes [C5Me5NiBr]2 and [C5Me5RhI2]2 react stepwise with P(OMe)3 by cleavage of the halide bridges and a subsequent Michaelis-Arbuzov-type reaction to give the neutral compounds C5Me5Ni[P(O)(OMe)2][P(OMe)3] (3) and C5Me5RhI[P(O)(OMe)2][P(OMe)3 (6). Treatment of 6 with an equimolar amount of NaI gives the sodium salt of the {C5Me5RhI[P(O)(OMe)2]2}- anion Na[L] (7) isolated as an adduct with 0.6 NaI. Reaction 7 with H2SO4 in water leads to the formation of the protonated complex C5Me5RhI[P(O)(OMe)2][P(OH)(OMe)2] (8), from which on treatment with thallium acetylacetonate C5Me5RhI[P(O)(OMe)2]2TI (9) is obtained. The X-ray structural analysis of 9 reveals that the organometallic anion L- is coordinated as a bidentate ligand by the P = O oxygen atoms to thallium, L- also behaves as a bidentate chelating ligand in the complexes [L]2Mg(OH2)2 (12), [L]2Zn (13) and [L]2UO2 (14), whereas it is presumably coordinated as an O,O′,I-tripod ligand in the compounds [L]PtMe3 (10) and [L]2Cu (11). In acid solution 8 reacts with NaBPh4 to give the diphenylborane derivative LBPh2 (15).
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 4
    ISSN: 0009-2940
    Schlagwort(e): Dihydroanthracene ; Dihydroanthracene, butyl-substituted ; Tricarbonylchromium ; Chromium complexes ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The complexes [9,10-dihydroanthracene][tricarbonylchromium]n [9,10-DHA][Cr(CO)3]n [n = 1 (1), 2 (2)] and the related mono- and bis(tricarbonylchromium) complexes of 2,6- and 2,7-di-tert-butyl-9,10-dihydroanthrancene [2,6-DB-9,10-DHA][Cr(CO)3]n [n = 1 (3), 2 (4)] and [2,7-DB-9,10-DHA][Cr(CO)3]n [n = 1 (5), 2 (6)] have been prepared by heating the 9,10-DHA species in the presence of hexacarbonylchromium [Cr(CO)6]. Evidence for the existence of the complex [2,6,9-tri-tert-butyl-9,10-DHA][Cr(CO)3] (7) is also presented. The complexes have been characterised spectroscopically, and for complex 1 an X-ray crystallographic structure determination has been carried out. This complex adopts the unexpected structure in which the non-coordinated arene ring is bent towards the Cr(CO)3 moiety. The syntheses and spectroscopic characterisations of 2,6- and 2,7-di-tert-butylanthracene (2,6- and 2,7-DBA), 2,6- and 2,7-di-tert-butyl-9,10-dihydroanthracene (2,6-and 2,7-DB-9,10-DHA), 2,6,9-, 2,7,9-, and 2,7,10-tri-tert-butyl-9,10-dihydroanthracene (2,6,9-, 2,7,9- and 2,7,10-TB-9,10-DHA), and 2,6,9,10- and 2,7,9,10-tetra-tert-butyl-9,10-dihydroanthracene(2,6,9,10- and 2,7,9,10-TeB-9,10-DHA) are also given.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 5
    ISSN: 0009-2940
    Schlagwort(e): Ferrocenes ; Cyclopentadienes, disilyl- ; Silatropic rearrangement ; Lithium cyclopentadienides ; Metallocene, trinuclear, mixed-metal ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The tetrahydro-4,4,8,8-tetramethyl-4,8-disila-s-indacenyl anion (LH) reacts with or without cyclopentadienyl anion (Cp-) and Fe2Cl4(THF)3 to give the mixed ferrocenes CpFe(LH) and (LH)2Fe in 50 and 63% yield, respectively. Near room temperature and in solution CpFe(LH) exists as a pair of enantiomers (syn-3a/b). According to an X-ray analysis both enantiomers are present in a single crystal. Compound 3 consists of a ferrocene linked to a cyclopentadiene by two Me2Si groups such that the acidic Cp proton points towards the iron. Temperature-dependent NMR spectra show that syn-3a and syn-3b are non-rigid molecules which are interconverted by 1,2-silatropic bond shifts (Ea = 49.2 ± 2.9 kJmol-1). Three more isomers (anti-3a, anti-3b, and the spiro derivative 3c), though present only in low concentration, are engaged in the rearrangement. (LH)2Fe is also non-rigid and exists as a pair of diastereomers (4a and 4b). The isomers of 3 and 4 undergo hydrolysis (e.g., syn-3a/3b gives [(Me2SiOSiMe2)Cp]FeCp (5) among others) and deprotonation. The latter yields CpFe(L-) (7) and (L-)2Fe (8), which are characterized by NMR spectroscopy. 7 forms crystals with [Li(TMEDA)]+ as counterion, and an X-ray analysis shows that lithium and iron are located at opposite sides of the strongly folded ligand L. The reaction of 7 with CrCl2(THF) gives the trinuclear stacked metallocene 9 in 47% yield. 9 has two unpaired electrons which are located essentially in the center of the molecule.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 6
    ISSN: 0009-2940
    Schlagwort(e): Gold(I) complex ; Phosphine (selenide) complexes ; Aus···Au interactions ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: [(CO)AuCl] reacts with equimolar amounts of Ph2PCH2P(Se)Ph2 (dpmSe) to afford ClAuPh2PCH2P(Se)Ph2, in which dpmSe is bound to gold in a monodentate fashion by phosphorus. Subsequent reaction of this 1:1 complex with AgClO4 results in the formation of the 10-membered ring complex 4 which crystallizes in the monoclinic space group P21/n with approximately centrosymmetric dicationic units, in which two gold (I) atoms are doubly bridged by two dpmSe ligands coordinated by phosphorus and selenium. The coordination at the gold atoms deviates from linearity and implies an Au···Au interaction with the gold(I) atoms separated by a distance of 3.020(1) Å.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 7
    ISSN: 0009-2940
    Schlagwort(e): Germanium(II) complexes ; Electron pair, „inert“ ; Spiro compounds ; Molecular fluctionality ; Phosphanylmethanide ligands ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Ring Expansion of Spirocyclic Germanium(II) Di(phosphanyl)methanide Complexes by Insertion of Sulfur and Selenium into Germanium-Phosphorus BondsGermanium in the intermolecularly stabilized germylene derivative Ge[C(PMe2)2(SiMe3)]2 (2a) is not oxidized by sulfur but the latter inserts 1 to 4 chalcogenide atoms into the Ge-P bonds of the four-membered chelate (4/4-) rings to give 4/5-, 5/5-, 5/6, and 6/6-membered spirocycles Ge[C2(SPMe2)n(PMe2)4-n(SiMe3)2] (n = 1-4: 4, 5a, 6, 7). Only 5a and 7 could be obtained in pure form, whereas compounds 4 and 6 with odd-numbered chalcogenide atoms are only characterized in solution, where they exist in equilibrium with 2a and 5a or 5a and 7, respectively. All these molecules are fluctional in solution. 7 is also obtained from GeCl2 · dioxane and Li[C(SPMe2)2(SiMe3)]. The selenium compound Ge[C(SePMe2)(PMe2)(SiMe3)]2 (5b) is obtained from 2a and grey selenium in toluene. An X-ray structure determination of 5b shows a distorted sphenoidal arrangement [approximate C2 symmetry of a spirocyclic germanium center within two five-membered rings containing a nearly linear Se-Ge-Se unit (Ge-Se 2.712/2.769(1) Å)]. The angle PGeP is 95.9(1)°. A bonding model with a stereochemically non-active electron lone pair at the formal germanium(II) center may account for this geometry. As byproducts in the sulfurization reactions, bis-(phosphanyl)methane disulfides are also observed in certain cases, from which H2C(SPMe2)2 has been isolated in pure form and characterized structurally.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 8
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 123 (1990), S. 1001-1004 
    ISSN: 0009-2940
    Schlagwort(e): Amino acid complexes ; L-Glutamate complexes ; Hydrogen L-glutamate complexes ; Potassium hydrogen L-glutamate ; Hydrogen bonding ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The title compound is obtained by neutralization of aqueous solutions of L-glutamic acid with potassium hydroxide, and crystallization from aqueous methanol. The compound shows a pH of 7 in water at ambient temperature and an optical rotation [α]20D of -4.30 (c = 3.0). In the crystal (orthorhombic, space group P212121) the potassium ion is in a distorted trigonal-prismatic environment of six oxygen atoms of four different amino acids and of the water molecule. No nitrogen coordination is observed. Through the bridging function of some of the α-carboxylate oxygen atoms (O1, O2) and through complexation of the metal through the γ-carboxylate groups (O3), a layer-coordination polymer, with strings of potassium ions running parallel, is formed. The layers are cross-linked by hydrogen bonds involving the ammonium and γ-carboxylate functions as well as the water molecule.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 9
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 275-278 
    ISSN: 0009-2940
    Schlagwort(e): Phosphane-borane adducts ; Diphosphinomethane ; Tripodal phosphane ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The tris(borane) adduct MeC(CH2PMe2BH3)3 (2) of 1,1,1-tris-[(dimethylphosphino)methyl]ethane has been prepared from the tripodal phosphane and Me2S-BH3 as the borane source. The crystal structure of 2·1/2 toluene has been determined by single-crystal X-ray diffraction methods. The molecules display crystallographic C3 symmetry and an overall staggered conformation. In an analogous way the bis(borane) adduct CH2(PH2BH3)2 (3) of 1,3-diphosphapropane has been synthesized, which decomposes above 50°C to give insoluble products, whose elemental analysis indicated that termal P-C bond cleavage is more frequent than P-B bond cleavage.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 10
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 1017-1023 
    ISSN: 0009-2940
    Schlagwort(e): Borates, triorgano-oxy, potassium salts ; N-Lewis base - diorgano(silyloxy)boranes ; Bicyclo[2.2.1]heptanes, heteroatom-containing, diastereomeric ; P-Lewis base - triorganoboranes, monocyclic, unsaturated ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: OrganosubstitutedBicyclic and Monocyclic Compounds from 2,5-Dihydro-1,2,5-oxasilaboratolates1a)The potassium salts of the cyclic anions of (A: R, R′ = CH3; B: R = C2H5, R′ = CH3; C: R = C6H5, R′ = CH3 react with [(CH3)2NCH2]Br in THF to yield the bicyclic compounds 1a (X-ray crystal structure analysis), 1b/1b' (endo/exo-C2H5), and 1c/1c' (endo/exo-C6H5). D (R=CH3, R'=C6H5) reacts with [(CH)32NCH2]Br to form a 1:4 mixture of 1d together with the heterocycle (3d) with elimination of (CH3)2N-C3H7. - From A - D and CIP(C6H5)2 the six-membered heterocycles (2a-d) are obtained in yields of ca. 90%.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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