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Tetrazine Chelate Ligands Bridging Two [Ru(acac)(2)] Fragments: Mixed Valency and Radical Complex Formation

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    0558484 - ÚFCH JH 2023 RIV DE eng J - Journal Article
    Kaim, W. - Löw, I. - Ringenberg, M. R. - Schwederski, B. - Filippou, V. - Fiedler, Jan
    Tetrazine Chelate Ligands Bridging Two [Ru(acac)(2)] Fragments: Mixed Valency and Radical Complex Formation.
    Zeitschrift für anorganische und allgemeine Chemie. Roč. 648, č. 23 (2022), č. článku e202200152. ISSN 0044-2313. E-ISSN 1521-3749
    R&D Projects: GA ČR(CZ) GA19-03160S
    Institutional support: RVO:61388955
    Keywords : diruthenium complexes * ruthenium * epr * l=3-amino-6-(3,5-dimethylpyrazol-1-yl)-1,2,4,5-tetrazine * acetylacetonate * superexchange * coordination * Crystal structure * Cyclic voltammetry * Diruthenium compounds * EPR spectroscopy * Spectroelectrochemistry
    OECD category: Physical chemistry
    Impact factor: 1.4, year: 2022
    Method of publishing: Open access

    Using bis(3-methyl-2-pyridyl)-1,2,4,5-tetrazine 1, 3-(2-pyrimidyl)-6-methyl-1,2,4,5-tetrazine 2 and bis(2-pyrimidyl)-1,2,4,5-tetrazine=bmtz as ligands, the complexes 3=[Ru(acac)(2)(1)], 4={[Ru(acac)(2)](2)(1)], 5={[Ru(acac)(2)](2)(bmtz)], and 6={[Ru(acac)(2)](2)(2)] were prepared and identified by structure analysis of crystallized material. The one-electron oxidized form 6(PF6) was also studied structurally, suggesting a Class II mixed-valent situation. The neutral dinuclear systems exhibit two reversible oxidation processes with comproportionation constants 10(9.2)<K-c<10(14.1) and one reduction which were analyzed UV/vis/NIR and EPR spectroscopically. Oxidation produces largely metal-based mixed-valent cations with very weak intervalence absorptions in the near IR whereas the electron uptake occurs at the tetrazine acceptor.
    Permanent Link: http://hdl.handle.net/11104/0332128

     
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