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 ASEP 0385239 Druh ASEP J - Článek v odborném periodiku Zařazení RIV J - Článek v odborném periodiku Poddruh J Článek ve WOS Název 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- 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. 9273-9281Poč.str. 9 s. Jazyk dok. eng - angličtina Země vyd. US - Spojené státy americké Klíč. slova DINUCLEAR RUTHENIUM COMPLEXES ; MOLECULAR-ORBITAL METHODS ; ANION-RADICAL COMPLEXES Vědní obor RIV CF - Fyzikální chemie a teoretická chemie CEP LD11086 GA MŠMT - Ministerstvo školství, mládeže a tělovýchovy Institucionální podpora UFCH-W - RVO:61388955 UT WOS 000308258700023 DOI 10.1021/ic300809w Anotace Neutral 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. Pracoviště Ústav fyzikální chemie J.Heyrovského Kontakt Michaela Knapová, michaela.knapova@jh-inst.cas.cz, Tel.: 266 053 196 Rok sběru 2013
Počet záznamů: 1