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  • 1
    ISSN: 0947-6539
    Keywords: crystal structure ; cyclophanes ; electrochemistry ; porphyrazines ; tetrathiafulvalenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrazinoporphyrazine system 13 (metal-free, zinc and copper derivatives) has been synthesised by tetramerisation of 2,3-dicyanopyrazine monomer unit 10. The structure of 13a-c has been established by 1H NMR spectroscopy, UV/Vis spectrophotometry, MALDI-TOF mass spectrometry, cyclic voltammetry and differential pulse voltammetry. The electrochemical redox behaviour of 13a-c is strongly solvent dependent. The expected two-stage oxidation of the tetrathiafulvalene (TTF) units of 13a-c was observed in a range of solvents; in addition, oxidation and reduction of the pyrazinoporphyrazine core of the metal-free derivative 13a was detected in benzonitrile. On excitation of 13 in the Q-band region no fluorescence was observed, which is presumably the consequence of intramolecular charge transfer between the TTF moieties and the excited state of the central porphyrazine. Molecular modelling studies on 13a and 13c are reported. During the course of this work, the novel TTF macrocycles 11 and 20 were synthesised; their X-ray crystal structures reveal severely bent TTF units, the conformations of which are discussed in detail. The X-ray crystal structures of the bis(1,3-dithiole) systems 15 and 18 have also been determined.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 564 (1988), S. 129-134 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Crystal and Molecular Structure of 15N-Nitridodichlorotris(dimethylphenylphenylphosphine)technetium(V)The title compound Tc15NCl2(Me2PhP)3 I has been prepared by the reaction of mer-TcCl3(Me2PhP)3 with Na15N3. The crystal structure of I has been determined by single crystal X-ray diffraction methods at room temperature. Crystals are orthorhombic, space group Pbca, with a = 16.663(1), b = 19.219(1), c = 16.769(1) Å and Z = 8. The technetium atom is six-coor-dinate. The coordination geometry is that of a distorted octahedron with 3 phosphine ligands in meridional positions. The strong trans influence of the nitrido ligand has been noted. The Tc—Cl length trans to N is 2.665(1) Å while those trans to P is 2.441(1) Å.
    Notes: Die Titelverbindung Tc15NCl2(Me2PhP)3 I wurde durch Reaktion von mer-TcCl3(Me2PhP)3 mit Na15N3 dargestellt und ihre Kristall- und Molekülstruktur durch Röntgenstrukturanalyse ermittelt. Die Kristalle sind orthorhombisch, Raumgruppe Pbca, mit a = 16,663(1), b = 19,219(1), c = 16,769(1) Å und Z = 8. Das Technetiumatom hat verzerrt oktaedrische Koordinationsgeometrie mit meridionaler Anordnung der Phosphine. Infolge des ausgeprägten trans-Effektes des Nitridoliganden ist der Tc—Cl-Bindungsabstand in trans-Stellung zum Nitridoliganden um 0,22 Å größer als jener, der sich in trans-Stellung zum Phosphinliganden befindet.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Preparation and Crystal and Molecular Structure of Tris(diethyldithiocarbamato)dimethylphenylphosphinetechnetium (III)The title compound Tc(S2CNEt2)3(Me2PhP) I has been prepared by the reaction of TcCl3(Me2PhP)3 with NaS2CNEt2. The crystal structure of I has been determined by single-crystal X-ray diffraction methods at room temperature. Crystals are rhombic, space group P212121, with a = 8.708(1), b = 12.012(1), c = 29.626(3) Å and Z = 4. The compound consists of discrete I molecules. The technetium atom has a seven-coordinated environment which is best described as a distorted pentagonal bipyramid. The Tc - P distance (2.330(3) Å) is remarkably short compared with other technetium complexes with mono-dentate phosphine ligands.
    Notes: Die Titelverbindung Tc(S2CNEt2)3(Me2PhP) I wurde durch Reaktion von TcCl3(Me2PhP)3 mit NaS2CNEt2 dargestellt und ihre Kristall- und Molekülstruktur durch Röntgenstrukturanalyse ermittelt. Die Kristalle sind rhombisch, Raumgruppe P212121, mit a = 8,708(1), b = 12,012(1), c = 29,626(3) Å und Z = 4. Die Verbindung besteht aus diskreten monomeren Molekülen. Das Technetiumatom hat siebenfache Koordination, die am besten als geringfügig verzerrte pentagonale Bipyramide beschrieben werden kann. Die Tc - P-Bindungslänge (2,330(3) Å) ist bemerkenswert kurz im Vergleich zu anderen Technetiumkomplexverbindungen mit einzähnigen Phosphanen.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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