Počet záznamů: 1  

Charged, but Found "Not Guilty": Innocence of the Suspect Bridging Ligands [RO(O)CNNC(O)OR](2-) = L2- in [(acac)(2)Ru(mu-L)Ru(acac)(2)](n), n = +,0,-,2-

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    SYSNO ASEP0385239
    Druh ASEPJ - Článek v odborném periodiku
    Zařazení RIVJ - Článek v odborném periodiku
    Poddruh JČlánek ve WOS
    NázevCharged, but Found "Not Guilty": Innocence of the Suspect Bridging Ligands [RO(O)CNNC(O)OR](2-) = L2- in [(acac)(2)Ru(mu-L)Ru(acac)(2)](n), n = +,0,-,2-
    Tvůrce(i) Roy, S. (DE)
    Sarkar, B. (DE)
    Imrich, H.-G. (DE)
    Fiedler, Jan (UFCH-W) RID, ORCID
    Záliš, Stanislav (UFCH-W) RID, ORCID
    Jimenez-Aparicio, R. (ES)
    Urbanos, F. A. (ES)
    Mobin, S. M. (IN)
    Lahiri, G. K. (IN)
    Kaim, W. (DE)
    Zdroj.dok.Inorganic Chemistry. - : American Chemical Society - ISSN 0020-1669
    Roč. 51, č. 17 (2012), s. 9273-9281
    Poč.str.9 s.
    Jazyk dok.eng - angličtina
    Země vyd.US - Spojené státy americké
    Klíč. slovaDINUCLEAR RUTHENIUM COMPLEXES ; MOLECULAR-ORBITAL METHODS ; ANION-RADICAL COMPLEXES
    Vědní obor RIVCF - Fyzikální chemie a teoretická chemie
    CEPLD11086 GA MŠMT - Ministerstvo školství, mládeže a tělovýchovy
    Institucionální podporaUFCH-W - RVO:61388955
    UT WOS000308258700023
    DOI10.1021/ic300809w
    AnotaceNeutral diastereoisomeric diruthenium(III) complexes, meso- and rae-[(acac)(2)Ru(mu-adc-OR)Ru(acac)(2)) (acac(-) = 2,4-pentanedionato and adc-OR2- = dialkylazodicarboxylato = [RO(O)CNNC(O)OR](2-), R = tert-butyl or isopropyl), were obtained from electron transfer reactions between Ru(acac)(2)(CH3CN)(2) and azodicarboxylic acid diallcyl esters (adc-OR). The mew,P isomer 3 with R = isopropyl was structurally characterized, revealing two deprotonated and N-N coupled carbamate functions in a reduced dianionic bridge with d(N-N) = 1.440(5) angstrom. A rather short distance of 4.764 angstrom has been determined between the two oxidized, antiferromagnetically coupled Ru-III centers. The rac isomer 4 with R = isopropyl exhibited stronger antiferromagnetic coupling. While the oxidation of the neutral compounds was fully reversible only for 3 and 4, two well-separated (10(8) < K-c < 10(10)) reversible one-electron reduction steps produced monoanionic intermediates 1(-)-4(-) with intense (epsilon approximate to 3000 M-1 cm(-1)), broad (Delta nu(1/2) approximate to 3000 cm(-1)) absorptions in the near-infrared (NIR) region around 2000 nm. The absence of electron paramagnetic resonance (EPR) signals even at 4 K favors the mixed-valent formulation Ru-II(adc-OR2-)Ru-III with innocently behaving bridging ligands over the radical-bridged alternative Ru-II(adc-OR center dot-)Ru-II, a view which is supported by the metal-centered spin as calculated by density functional theory (DFT) for the methyl ester model system. The second reduction of the complexes causes the NIR absorption to disappear completely, the EPR silent oxidized forms 3(+) and 4(+), calculated with asymmetrical spin distribution, do not exhibit near infrared (NIR) activity.
    PracovištěÚstav fyzikální chemie J.Heyrovského
    KontaktMichaela Knapová, michaela.knapova@jh-inst.cas.cz, Tel.: 266 053 196
    Rok sběru2013
Počet záznamů: 1  

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