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First Crystal Structure Determination and High-Frequency EPR Study of an Organoarsanecopper Radical Complex

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    SYSNO ASEP0181781
    Document TypeJ - Journal Article
    R&D Document TypeJournal Article
    Subsidiary JOstatní články
    TitleFirst Crystal Structure Determination and High-Frequency EPR Study of an Organoarsanecopper Radical Complex
    Author(s) Ye, S. (DE)
    Kaim, W. (DE)
    Sarkar, B. (DE)
    Schwederski, B. (DE)
    Lissner, F. (DE)
    Schleid, T. (DE)
    Duboc-Toia, C. (FR)
    Fiedler, Jan (UFCH-W) RID, ORCID
    Source TitleInorganic Chemistry Communications. - : Elsevier - ISSN 1387-7003
    Roč. 6, - (2003), s. 1196-1200
    Number of pages5 s.
    Languageeng - English
    CountryNL - Netherlands
    Keywordsarsane ligands ; copper complex ; EPR
    Subject RIVCF - Physical ; Theoretical Chemistry
    R&D ProjectsGA203/03/0821 GA ČR - Czech Science Foundation (CSF)
    OC D15.10 GA MŠMT - Ministry of Education, Youth and Sports (MEYS)
    CEZAV0Z4040901 - UFCH-W
    AnnotationThe red radical complex {(mu-bptz)[Cu(AsPh3)(2)](2)}(BF4) 1, bptz=3,6-bis(2-pyridyl)-1,2,4,5-tetrazine, was obtained as a stable species and characterized by X-ray crystallography, spectroelectrochemistry and EPR at 9.5 and 285 GHz. Comparison with the previously reported {(mu-bptz)[Cu(PPh3)(2)](2)}(BF4) 2 reveals longer Cu-element bonds by about 0.1 Angstrom but otherwise a similar "organic sandwich" structure involving intramolecular pi(phenyl)-pi(tetrazine)-pi(phenyl) interactions, a 3+1 coordination at the copper(I) centers, and averaged tetrazine intraring bond distances. Reversible oxidation to a blue dication with an intense MLCT band at 650 nm occurs at -0.24 V vs. Fc(+/o). EPR studies show the effect of the higher spin-orbit coupling constant of the As vs. P atoms through slightly larger g anisotropy as determined through high frequency measurements. (C) 2003 Elsevier B.V. All rights reserved.
    WorkplaceJ. Heyrovsky Institute of Physical Chemistry
    ContactMichaela Knapová, michaela.knapova@jh-inst.cas.cz, Tel.: 266 053 196
    Year of Publishing2004

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