ALBERT

All Library Books, journals and Electronic Records Telegrafenberg

Your email was sent successfully. Check your inbox.

An error occurred while sending the email. Please try again.

Proceed reservation?

Export
Filter
  • General Chemistry  (611)
  • ab initio calculations  (44)
  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    ISSN: 0947-6539
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    ISSN: 0947-6539
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 3
    ISSN: 0947-6539
    Keywords: asymmetric catalysis ; aziridines ; chiral ligands ; palladium compounds ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The chiral palladium π-allyl intermediate for the catalytic asymmetric synthesis shown in Scheme 1 has been isolated as the PF-6 salt. MM 2 calculations have been performed and the structure of the palladium complex in solution has also been investigated by means of NMR spectroscopy. Both the computational and spectroscopic results suggest that in the complex the bidentate bis(aziridine) ligand adopts a conformation that forces the π-allyl moiety out of the normally preferred square-planar geometry. This nicely explains the very high enantioselectivity observed in the title reaction.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 4
    ISSN: 0947-6539
    Keywords: alkoxides ; clusters ; Group 15 complexes ; Lewis acids ; oxygen bridges ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: As(OtBu)3 does not form adducts with alkali metal tert-butoxides MOtBu (M = Li, Na, K, Rb and Cs), whereas the corresponding Sb(OtBu)3 (2) and Bi(OtBu)3 (3) react with MOtBu (M = K, Rb, Cs) to yield M(OtBu)4Sb (M = K (6), Rb (7), Cs (8)) and M(O-tBu)4Bi (M = 9), respectively. X-ray structure determinations for 6 and 9 show them to be one-dimensional coordination polymers composed of E(OtBu)4 (E = Sb, Bi) units linked through potassium atoms. These E(OtBu)4 units display a ψ-trigonal-bipyramidal coordination around the metal atom (Sb—O = 1.971(2) and 2.181(2) Å, Bi—O = 2.068(8) and 2.275(8) Å). Both the structures exhibit a planar four-coordinate environment of oxygen around the potassium atoms (K—O = 2.650(2)-2.967(2) Å in 6, 2.53(1)-3.15(1) Å in 9). Compound 2 reacts with two equivalents of KOtBu to afford K2Sb(OtBu)5 · dioxane (10), which contains Sb2K2O5 cage units and can be described as an O5 trigonal bipyramid with metal atoms inserted in the equatorial edges. Each metal atom is tetracoordinated by oxygen atoms of the cage (Sb—O = 1.979(3)-2.144(3) Å. K—O = 2.592(3)-2.778(2) Å). The dioxane molecules increase the coordination number at each potassium atom to five by forming bridges between the molecules through K—O bonds. Reaction of 2 and 3 with NaOtBu produce the cluster compounds Na4Sb2O(OtBu)8 (4) and Na4Bi2O-(OtBu)8 (5) in high yields. K4Sb2O-(OtBu)8 (11) is obtained in almost quantitative yield by heating KSb(OtBu)4 in benzene for 24 h. Compounds 4, 5 and 11 crystallise in rhombohedral lattices; the crystal structure analyses show a superposition of molecules. With an isotropic oxygen-centred M6 octahedron. The formation of these oxo-tert-butoxides is accompanied by evolution of isobutene. Addition of four equivalents of THF to 11 gives K4Sb2O(OtBu)8 · 4 THF (12). X-ray diffraction studies reveal a cis arrangement of the Sb atoms in the central OSb2K4 unit. K4Sb2O2(OiPr)12 (13) is obtained as the major product on heating KSb(OtBu)4 and subsequent reaction with isopropyl alcohol. In the crystal structure, two oxygen-centred Sb2K2 tetrahedra (K—O 2.693(4) Å, Sb—O = 1.982(5) Å) linked through iPrO—K bonds (2.726(7)-2.738(7) Å) are observed. In the reactions of KSb(OtBu)4 (6) with the metal halides CaCl2, TlCl and CuI, a halide ion is transferred to potassium; this results in formation of potassium halide, the corresponding alkoxide and Sb(OtBu)3.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 5
    ISSN: 0947-6539
    Keywords: amethyrin ; orangarin ; porphyrinoids ; terpyrroles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new, general synthesis of the first β-substituted tetra- and hexaalkyl terpyrroles is described. Also described are two new classes of expanded porphyrins derived from the hexaalkyl terpyrrole. The key step in the terpyrrole formation is the copper(II)-mediated oxidative coupling of the LDA-derived enolates of α-keto pyrroles. The first new expanded porphyrin reported here, the so-called “orangarin”, contains five pyrrolic subunits and two bridging carbon atoms, and is formally a 20π-electron nonaromatic macrocycle. The second new class of expanded porphyrins, the “amethyrins”, are 24π-electron nonaromatic macrocycles containing six pyrrole units. Both of these new macrocycles, as well as one of the new terpyrrolic precursors have been structurally characterized by single crystal X-ray diffraction analysis.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 6
    ISSN: 0947-6539
    Keywords: chelate ligands ; hydrogen bonds ; ligand design ; mass spectrometry ; stability constants ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of compounds containing the mononuclear complexes [M(tdci)2]3+ (tdci = 1,3,5-trideoxy-1,3,5-tris(dimethylamino)-cis-inositol, M = Al, Fe, Ga, In) and [M(tdci)2]4+ (M = Ti, Ge, Sn) was prepared and characterized by elemental analysis, NMR spectroscopy, and FAB mass spectrometry. Characteristic fragmentation reactions in the mass spectra were elucidated. X-ray analysis of the AlIII, FeIII, GaIII, and InIII complexes revealed that two neutral, zwitterionic tdci ligands coordinate to the metal cation exclusively through deprotonated alkoxo groups. The six coordinated oxygen donors and the six N—H protons form a hydrophilic pocket, whereas the two cyclohexane rings and the twelve methyl groups form two hydrophobic shells. The hydrophilic pocket is filled with twelve water molecules, which are arranged as a second and a third coordination sphere around the metal cation. The reactivity in aqueous solution was investigated by potentiometric measurements. The bis complexes proved to be stable at pH 7. The evaluated formation constants show an increase of stability in the order AlIII〈InIII〈GaIII〈FeIII. The measurements established that tdci is one of the most effective tridentate ligands for small (r ≤ 0.8Å) and highly charged cations. The different chelating properties of tdci and of the unmethylated 1,3,5-triamino- 1,3,5-trideoxy-cis-inositol are discussed in terms of different steric requirements and different types of solvation of the corresponding complexes in aqueous solution.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 7
    ISSN: 0947-6539
    Keywords: charge transfer ; EPR spectroscopy ; organometallic compounds ; platinum compounds ; spectroelectrochemistry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In spite of their very similar cyclic voltammograms, absorption spectra, and solvatochromic behavior, the two 1,4-diazabutadiene title complexes exhibit markedly different photoreactivities and underlying electronic structures, as evident from absorption and EPR spectra of the persistent anion radical forms. The lowest excited state of the nonphotoreactive PtII system [(CyN=CH—CH=NCy)-PtMe2] has MLCT (metal-to-ligand charge-transfer, 5d → π*) character, and the EPR spectrum of the corresponding anion radical at 〈g〉 = 2.016 exhibits sizable metal/ligand orbital mixing. On the other hand, the structurally characterized PtIV complex [(CyN=CH—CH=NCy)-PtMe4] (C2/c; a = 2021.6(2), b = 805.3(1), c = 1254.2(1) pm; β = 111.05(1)°; V = 1905.7(4) × 106 pm3; Z = 4) has a lowlying photoreactive LLCT (ligand-to-ligand charge-transfer, σPt—C → π*) excited state in which the axial Pt—C bonds are activated, as already suggested by the longer Pt—C(ax) bonds (214.0(8) pm) relative to Pt—C(eq) in the ground state (204.5(5) pm). The anion radical of the PtIV complex has lost the long-wavelength absorption band in the visible; it shows a well-resolved EPR spectrum at 〈g〉 = 1.9945 with π-ligand and 195Pt hyperfine structure and a small g anisotropy. A qualitative MO scheme is presented to account for the similar frontier-orbital energy differences despite dissimilar underlying electronic structures.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    ISSN: 0947-6539
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 9
    ISSN: 0947-6539
    Keywords: alkyne complexes ; carbon networks ; macrocycles ; platinum compounds ; tetraethynylethene ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The syntheses of the first organometallic mono- and dinuclear platinum complexes bearing the tetraethynylethene unit as an η1-ligand are reported. Structural characterization of two of the trans σ-bis(acetylide) derivatives by X-ray crystallography reveals coplanarity of the acetylenic π-ligands and indicates possible electronic delocalization across the metal center. This notion is further supported by comparing the electronic absorption spectra of the platinum-containing compounds with those of related tetraethynylethene derivatives without metals. The solidstate structure of a dinuclear complex with two iodoplatinum fragments attached to one set of geminal acetylenes of tetraethynylethene was also investigated by X-ray diffraction. Hay coupling of a mononuclear species leads to the incorporation of the σ-bis(acetylide) moiety into a diplatinated metallacycle. This macrocyclic compound represents a novel structural motif in the design of a transition metal linked carbon network based on tetraethynylethene.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 10
    ISSN: 0947-6539
    Keywords: calixarenes ; cavitands ; molecular modeling ; resorcinarenes ; supramolecular chemistry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Coupling reactions of calix[4]arenes and modified resorcin[4]arenes have been investigated. Reaction of mono(chloroacetamido)calix[4]arene 4 with tetrahydroxycavitand 9 gave the 1:1 coupled product 13 in 61% yield. Combination of upper-rim 1,3-difunctionalized calix[4]arene 5 with 9 afforded predominantly the 2:1 calix-resorcinarene 18 in 47% yield. Reaction of 1,2-difunctionalized calix[4]arene 6 with 9 gave five products, namely, endo 1:1 (19), exo 1:1 (20), endo-endo 2:1 (21), endo-exo 2:1 (22), and exo-exo 2:1 (23) in ratios that depend on the reaction conditions. The stereochemistry of the different products was determined with NOESY experiments. The structures of 21 a and 23 b were calculated by using molecular mechanics, which revealed that intramolecular hydrogen bonds are only present in the former. Reaction of 1,2-bis(chloroacetamido)calix[4]arene 26, which has two additional nitro groups at the remaining aromatic rings, with 9 yielded three different products, namely, endo 1:1 (28), endo-endo 2:1 (30), and endo-exo 2:1 (32) in ratios that depend on the reaction conditions. There is a preference for the endo orientation in the formation of the 1:1 coupled product, probably owing to an interaction of the nitro groups with the cavitand in the transition state. After conversion of the nitro groups in 28 into chloroacetamido moieties, reaction with Cs2CO3 in DMF under high-dilution conditions afforded holand 33 in 26% yield together with calix[4]arene-based carceplex 34 with an encapsulated DMF molecule (27% yield). Holand 33 was obtained in 33% yield by reaction of the tetrakis(chloroacetamide) endo-endo 2:1 isomer 31 with tetrahydroxycavitand 9. Holand 33 contains a cavity of nanosize dimensions. Molecular mechanics simulations indicate that holand 33 adopts a conformation with eight hydrogen bonds and a large, preorganized cavity with two entrances of smaller dimensions. Molecular dynamics simulations of holand 33 in both CHCl3 and THF showed that four solvent molecules can be accommodated in the cavity at well-defined positions.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
Close ⊗
This website uses cookies and the analysis tool Matomo. More information can be found here...