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  • 1
    Electronic Resource
    Electronic Resource
    Metal Complexes with Tetrapyrrole Ligands, LXI. Structure and Products of Electrochemical Oxidation of Zirconium(IV) and Hafnium(IV) Bisporphyrinate Double-Deckers (1992)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 125 (1992), S. 107-115 
    Details
    ISSN: 0009-2940
    Keywords: Zirconium porphyrins ; Hafnium porphyrins ; Porphyrin double-deckers ; Metal bisporphyrinates ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electrochemical oxidation of zirconium and hafnium double-deckers M(P)2 (M=Zr, Hf; P=OEP, TPP) (Scheme 1)2) leads to mono- and dications which show near infrared absorption bands which are of ≈ 2000 cm-1 higher energy than those of the corresponding cerium double-decker cations. [Zr(OEP)2]X, [Zr(OEP)2]X2, and [Zr(TPP)2]X (X=ClO4- and PF6-) are isolated after electrochemical oxidation and are characterized by IR and NMR spectroscopy. Magnetic susceptibility measurements (2 K 〈 T 〈 300 K) of the solids confirm the strong coupling of the electron spins in the diamagnetic dication salt [Zr(OEP)2][ClO4]2. The molecular structure of Zr(OEP)2 is elucidated by an X-ray structural analysis.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19921250118
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  • 2
    Electronic Resource
    Electronic Resource
    Metal Complexes with Tetrapyrrole Ligands, LVIII. Zirconium(IV) and Hafnium(IV) Bisporphyrinate Double Deckers: Synthesis, Spectra, Redox Potentials, and Structure (1991)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 1051-1058 
    Details
    ISSN: 0009-2940
    Keywords: Zirconium porphyrins ; Hafnium porphyrins ; Porphyrin double deckers ; Metal bisporphyrinates ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of new zirconium and hafnium bisporphyrinate double deckers M(P)2 (M=Zr, Hf; P=OEP, TPP)2,3) is described. The complexes are characterized by UV/Vis/NIR and 1H-NMR spectroscopy and cyclic voltammetry. As compared with M=Ce, the redox potentials or the energies of the nearinfrared absorption bands of the corresponding radical cations [M(P)2]+ are lower by ≍ 0.2 V or higher by ≍ 2000 cm-1, respectively, Hence, there is a stronger π-π interaction between the porphyrin ligands as compared with the cerium analogues due to the smaller ionic radii of Zr(IV) and Hf(IV). X-ray crystallography of Zr(TPP)2 confirms the sandwich-like structure of the compound and the close proximity of the porphyrin ligands.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19911240511
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  • 3
    Electronic Resource
    Electronic Resource
    Complexation Studies with a Calix[4]arene-Derived Phosphinite - Divergent Arrays of Cavities Linked by MCl2 Fragments (M = Pd, Pt) (1998)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 451-457 
    Details
    ISSN: 1434-1948
    Keywords: Calixarene ; Phosphinite ; Calixphosphane ; Transition metals ; X-ray diffraction ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A cone-shaped calix[4]arene-derived monophosphinite, 25,27-di(ethoxycarbonylmethoxy)-26-hydroxy-28-(diphenylphosphinooxy)calix[4]arene (L1), has been prepared in two steps from calix[4]arene. Treatment of L1 with [AuCl(tetrahydrothiophene)] in tetrahydrofuran gave the phosphinite complex [AuClL1] (1). Reaction of [PdCl2(PhCN)2] with two equivalents of L1 gave selectively trans-[PdCl2L12] (2). Complex 2 · 2 CH2Cl2 crystallizes in the triclinic space group P1¯. The molecule is centrosymmetric, leading to a divergent array of the two calixarene moieties. The palladium atom resides outside both cones. As a result of steric interactions, the meta and para carbon atoms of the PPh2-bearing aryl ring are significantly pushed to the interior of the cavity. The related platinum complex trans-[PtCl2L122] (3), was obtained similarly from [PtCl2(PhCN)2] and presents in the solid state a structure which is isomorphous to that of 2. The diphosphinite 25,27-di(ethoxycarbonylmethoxy)-26,28-bis(diphenylphosphinoxy)calix[4]arene (cone) (L2) has also been prepared and reacts with [PtCl2(PhCN)2] to yield oligomeric material.
    Type of Medium: Electronic Resource
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