View : 16 Download: 8

Mechanistic insight into catalytic oxidations of organic compounds by ruthenium(iv)-oxo complexes with pyridylamine ligands

Title
Mechanistic insight into catalytic oxidations of organic compounds by ruthenium(iv)-oxo complexes with pyridylamine ligands
Authors
Ohzu S.Ishizuka T.Hirai Y.Jiang H.Sakaguchi M.Ogura T.Fukuzumi S.Kojima T.
Ewha Authors
Shunichi Fukuzumi
SCOPUS Author ID
Shunichi Fukuzumiscopus
Issue Date
2012
Journal Title
Chemical Science
ISSN
2041-6520JCR Link
Citation
vol. 3, no. 12, pp. 3421 - 3431
Indexed
SCI; SCIE; SCOPUS WOS scopus
Abstract
A series of Ru(iv)-oxo complexes (4-6) were synthesized from the corresponding Ru(ii)-aqua complexes (1-3) and fully characterized by 1H NMR and resonance Raman spectroscopies, and ESI-MS spectrometry. Based on the diamagnetic character confirmed by the 1H NMR spectroscopy in D 2O, 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 (NH 4) 2[Ce IV(NO 3) 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 IVO complexes proceed via a concerted proton-coupled electron transfer mechanism. © 2012 The Royal Society of Chemistry.
DOI
10.1039/c2sc21195e
Appears in Collections:
자연과학대학 > 화학·나노과학전공 > Journal papers
Files in This Item:
001.pdf(550.6 kB)Download
Export
RIS (EndNote)
XLS (Excel)
XML


qrcode

Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.

BROWSE