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Synthesis, Reduction Chemistry, and Spectroscopic and Computational Studies of Isomeric Quinolinecarboxaldehyde Triosmium Clusters

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    0101028 - UFCH-W 20040018 RIV US eng J - Journal Article
    Rosenberg, E. - Rokhsana, D. - Nervi, C. - Gobetto, R. - Milone, L. - Viale, A. - Fiedler, Jan - Botavina, M. A.
    Synthesis, Reduction Chemistry, and Spectroscopic and Computational Studies of Isomeric Quinolinecarboxaldehyde Triosmium Clusters.
    [Syntéza, redukční chemie, spectroskopické a výpočetní studium isomerických chinolinekarboxaldehydových tříosmiových klastrů.]
    Organometallics. Roč. 23, - (2004), s. 215-223. ISSN 0276-7333. E-ISSN 1520-6041
    R&D Projects: GA ČR GA203/03/0821; GA MŠMT OC D15.10
    Institutional research plan: CEZ:AV0Z4040901
    Keywords : organometallic chemistry * radical-anions * density
    Subject RIV: CF - Physical ; Theoretical Chemistry
    Impact factor: 3.196, year: 2004

    The quinoline derivatives Os-3(CO)(n)(mu(m)-eta(2)-L-H)(mu-H) (L = quinoline-4-carboxaldehyde, n 10, m = 2, 4; n = 9, N-C(8) bound, m = 3, 5; n = 10, N-C(2) bound, m = 2, 6; L = quinoline-3-carboxaldehyde, n = 9, N-C(8) bound, m = 3, 7) are obtained by the reaction of Os-3(CO)(10)(CH3CN)(2) with the quinoline-3-carboxaldehyde or -4-carboxaldehyde ligand followed by photochemical decarbonylation in the case of 5 and 7. The quinoline-4-carboxaldehyde clusters and the free ligand all show reversible 1e(-) reductions, but the electron-deficient 5 shows two separate reversible 1e(-) reductions, the first at much less negative potential than for the previously investigated Os-3(Co)(9)(mu(3)-eta(2) -L-H)(mu-H) (L = phenanthridine, 1; L = 5,6-benzoquinoline, 2), while the free ligand is reduced at a more negative potential than any of the clusters. The spectroscopic properties of the clusters upon electrochemical and chemical reduction have been investigated.

    Chinolinové deriváty Os-3(CO)(n)(mu(m)-eta(2)-L-H)(mu-H ) (L = chinolin-4-carboxaldehyd, n = 10, m = 2, 4; n = 9, N-C(8 ) vazba, m = 3, 5; n = 10, N-C(2 ) vazba, m = 2, 6; L = chinolin-3-carboxaldehyd, n = 9, N-C(8 ) vazba, m = 3, 7 ) byly získány reakcí Os-3(CO)(10)(CH 3CN)(2) s chinolin-3-carboxaldehydovým nebo -4-carboxaldehydovým ligandem následovanou fotochemickou dekarbonylací v případě 5 a 7. Chinolin-4-carboxaldehydové klastry i volný ligand vykazují reverzibilní 1e(-) redukce, ale elektron-deficitní 5 vykazuje dvě oddělené reverzibilní 1e(-) redukce, první u mnohem méně negativního potenciálu než u dříve vyšetřovaného Os-3(Co)(9)(mu(3)-eta(2 ) -L-H)(mu-H) (L = phenanthridine , 1; L = 5,6-benzochinolin, 2), zatímco volný ligand se redukuje u negativnějšího potenciálu než kterýkoli z klastrů. Byly studovány spectroskopické vlastnosti klastrů po elektrochemické a chemické redukci.
    Permanent Link: http://hdl.handle.net/11104/0008501
     
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