Journal
CHEMICAL SCIENCE
Volume 3, Issue 12, Pages 3421-3431Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c2sc21195e
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Funding
- Japan Society of Promotion of Science (JSPS, MEXT) of Japan [20108010, 21350035, 22245028, 24245011]
- KOSEF/MEST through WCU of Korea [R31-2008-000-10010-0]
- Asahi Glass Foundation
- Iwatani Naoji Foundation
- National Research Foundation of Korea [R31-2012-000-10010-0] Funding Source: Korea Institute of Science & Technology Information (KISTI), National Science & Technology Information Service (NTIS)
- Grants-in-Aid for Scientific Research [20108010, 24655044, 20108001, 11J07254] Funding Source: KAKEN
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A series of Ru(IV)-oxo complexes (4-6) were synthesized from the corresponding Ru(II)-aqua complexes (1-3) and fully characterized by H-1 NMR and resonance Raman spectroscopies, and ESI-MS spectrometry. Based on the diamagnetic character confirmed by the H-1 NMR spectroscopy in D2O, the spin states of 5 and 6 were determined to be S = 0 in the d(4) configuration, in sharp contrast to that of 4 being in the S = 1 spin state. The aqua-complexes 1-3 catalyzed oxidation of alcohols and olefins using (NH4)(2)[Ce-IV(NO3)(6)] (CAN) as an electron-transfer oxidant in acidic aqueous solutions. Comparison of the reactivity of electrochemically generated oxo-complexes (4-6) was made in the light of kinetic analyses for oxidation of 1-propanol and a water-soluble ethylbenzene derivative. The oxo complexes (4-6) exhibited no significant difference in the reactivity for the oxidation reactions, judging from the similar catalytic rates and the activation parameters. The slight difference observed in the reaction rates can be accounted for by the difference in the reduction potentials of the oxo-complexes, but the spin states of the oxo-complexes have hardly affected the reactivity. The activation parameters and the kinetic isotope effects (KIE) observed for the oxidation reactions of methanol indicate that the oxidation reactions of alcohols with the Ru-IV=O complexes proceed via a concerted proton-coupled electron transfer mechanism.
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