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Reversible Intramolecular Single-Electron Oxidative Addition Involving a Hemilabile Noninnocent Ligand
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SYSNO ASEP 0361464 Document Type J - Journal Article R&D Document Type Journal Article Subsidiary J Článek ve WOS Title Reversible Intramolecular Single-Electron Oxidative Addition Involving a Hemilabile Noninnocent Ligand Author(s) Hübner, R. (DE)
Weber, S. (DE)
Strobel, S. (DE)
Sarkar, B. (DE)
Záliš, Stanislav (UFCH-W) RID, ORCID
Kaim, W. (DE)Source Title Organometallics. - : American Chemical Society - ISSN 0276-7333
Roč. 30, č. 6 (2011), s. 1414-1418Number of pages 5 s. Language eng - English Country US - United States Keywords density-functional calculation ; order regular approximation ; non-innocent ligands Subject RIV CG - Electrochemistry R&D Projects KAN100400702 GA AV ČR - Academy of Sciences of the Czech Republic (AV ČR) LD11086 GA MŠMT - Ministry of Education, Youth and Sports (MEYS) CEZ AV0Z40400503 - UFCH-W (2005-2011) UT WOS 000288470900024 DOI 10.1021/om100969q Annotation Using the noninnocent ligand Q[= 4,6-di-tert-butyl-(2-methylthiophenylimino)-o-berizoquinone] with a thioether group as potential coordination function, it has been possible to substantiate a single-electron transfer induced oxidative addition;within the complex [IrCp*Q](0/+) (Cp* = C(5)Me(5)) via structural characterization (catecholato -> semiquinonato transition coupled with reversible S -> Ir coordination), via cyclic voltammetry, EPR, and DFT (semiquinone formulation with about 8% Ir participation). The intramolecular rearrangement of the 16-electron precursor [IrCp*Q] triggered by electron removal illuminates the complementary activities of the substrate binding metal and the electron-buffering ligand as was recently employed by Ringenberg et al. in dihydrogen activation (Organometallics 2010, 29, 1956). Workplace J. Heyrovsky Institute of Physical Chemistry Contact Michaela Knapová, michaela.knapova@jh-inst.cas.cz, Tel.: 266 053 196 Year of Publishing 2012
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