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  • 1
    Electronic Resource
    Electronic Resource
    Linear Five-Centred Chromium Multiple Bonds Bridged by Four tpda2- Ligands [tpda2- = tripyridyldiamido dianion] - Synthesis and Structural Studies (1999)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1243-1251 
    Details
    ISSN: 1434-1948
    Keywords: Metal string complexes ; Multicentered metal-metal multiple bond ; Quadruple bonds ; Metal-metal interactions ; Chromium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The linear pentanuclear chromium complexes [CrII5(μ5-tpda)4Cl2] (1), [CrII5(μ5-tpda)4(NCS)2] (2), [CrIIICrII4(μ5-tpda)4F2](BF4) (3), and [CrIIICrII4(μ5-tpda)4F(OTf)](OTf) (4), with four all-syn tri(α-pyridyl)diamido dianion (tpda2-) ligands, have been prepared and structurally characterized. Compounds 1 and 2 possess a delocalized Cr(II)-Cr(II)-Cr(II)-Cr(II)-Cr(II) five-centred metal-metal bond of order 1.5. In both 1 and 2 two values for CrII-CrII bond lengths are found both; the outer ones connected with axial ligands are 2.284(1) and 2.285(2) Å, and the inner ones are 2.2405(8) and 2.246(1) Å, for 1 and 2, respectively. When compound 1 reacts with 2 equiv. of AgBF4 or Ag(OTf), a oxidation reaction takes place and one of the terminal chromium(II) ions is oxidized to produce [CrIIICrII4(μ5-tpda)4F2]BF4 (3) or [CrIIICrII4(μ5-tpda)4F(OTf)](OTf) (4). Two short Cr-Cr distances [1.969(2) and 2.138(2) Å for 3, 1.846(1) and 1.922(1) Å for 4] are found, with the presence of two quadruple bonds among four adjacent CrII ions. The fifth CrIII ion, which is separated from the neighboring CrII ion by 2.487(2) Å for 3 and 2.610(1) Å for 4, is simply a square pyramidal unit with no metal-metal bonding interaction.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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