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  • 1
    Electronic Resource
    Electronic Resource
    Structure and conductivity of an electrocrystallized ruthenium [1,8]binaphthyridine complex (1996)
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 781-788 
    Details
    ISSN: 0947-6539
    Keywords: chelate ligands ; intermolecular interactions ; reductions ; ruthenium complexes ; semiconductors ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: For the first time, the crystal structure of a RuII binaphthyridine complex and that of its corresponding oneelectron reduced product are reported. Reductive electrocrystallization of [Ru-(binap-2)3](PF6)2 (1, where binap-2 = 3,3′-dimethylene -2,2′ - bi [1, 8] naphthyridine) from an acetonitrile solution resulted in the formation of dark blue crystals of the one-electron reduction product, [Ru-(binap-2)3](PF6) (2) having one fewer PF-6 per formula unit. X-ray analysis reveals that the reduced complex retains the three-ligand d6 coordination around the central RuII. Based on electrostatic considerations and the positions of the PF-6 anions in the lattice, the added electron appears to be delocalized over two nearly equivalent binap-2 ligands in 2, in marked contrast to monoreduced and electrocrystallized [Na ⊂ (trisbipyridyl cryptand)]0, in which the electron is localized on only one of the bipyridyl subunits. However, based on the available data, alternative interpretations are possible. The crystal packing diagram of 2 shows several intermolecular π-π interactions, with 12 of these being shorter than 3.5 Å. In contrast, there are no intermolecular distances shorter than 3.5 Å in the crystals of 1. Two-probe electrical conductivity measurements under anaerobic conditions indicate that the crystals of 2 behave as semiconductors with a band gap of 0.53 eV, while those of the unreduced compound are insulating. This represents the first molecular semiconducting material with the potential for bidimensional behavior of its kind.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/chem.1460020707
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    Paper (German National Licenses)
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  • 2
    Electronic Resource
    Electronic Resource
    Insertion Reactions into Palladium-Carbon Bonds of Complexes Containing Terdentate Nitrogen Ligands; Experimental and Ab initio MO Studies (1998)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 1129-1143 
    Details
    ISSN: 1434-1948
    Keywords: Insertion ; N ligands ; Terdentate ligands ; Rigid ligands ; Palladium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Novel methyl complexes [Pd(Me)(N-N-N)]X (N-N-N = flexible or rigid terdentate nitrogen ligand, X = Cl, SO3CF3, BAr′4) have been synthesized and fully characterized. All complexes readily underwent insertion of carbon monoxide resulting in the quantitative formation of complexes [Pd{C(O)Me}(N-N-N)]X [X = Cl (1d-6d), BAr′4 (1e-6e)]. Subsequently, complexes 2e-6e underwent quantitative insertion of norbornadiene, resulting in complexes [Pd{C7H8C(O)Me}(N-N-N)]BAr′4 (2f-6f). Unexpectedly, these complexes, including even those containing rigid terdentate nitrogen ligands, possess a structure in which the nitrogen ligand is coordinated in a bidentate fashion. A kinetic study of the reaction of norbornadiene with complexes 1e-6e revealed that the reactivity of complexes 1e-6e toward norbornadiene increases with increasing rigidity of the terdentate ligand, i.e. with increasing strain in the PdN3 moiety, which indicates that insertion very likely occurs via a mechanism involving nitrogen dissociation. This is fully supported by ab initio MO calculations on CO and ethylene insertion into carbon-palladium bonds of cationic model systems containing a rigid terdentate nitrogen ligand, which showed that the lowest-energy pathway for both insertion reactions consists of substitution of one of the distal nitrogen atoms of the rigid terdentate nitrogen ligand by the substrate, followed by a rate-determining migratory insertion of the substrate into the carbon-palladium bond.
    Type of Medium: Electronic Resource
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    Paper (German National Licenses)
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