Reversible Intramolecular Single-Electron Oxidative Addition Involving a Hemilabile Noninnocent Ligand

0361464 - ÚFCH JH 2012 RIV US eng J - Journal Article
Hübner, R. - Weber, S. - Strobel, S. - Sarkar, B. - Záliš, Stanislav - Kaim, W.
Reversible Intramolecular Single-Electron Oxidative Addition Involving a Hemilabile Noninnocent Ligand.
Organometallics. Roč. 30, č. 6 (2011), s. 1414-1418. ISSN 0276-7333. E-ISSN 1520-6041
R&D Projects: GA AV ČR KAN100400702; GA MŠMT LD11086
Institutional research plan: CEZ:AV0Z40400503
Keywords : density-functional calculation * order regular approximation * non-innocent ligands
Subject RIV: CG - Electrochemistry
Impact factor: 3.963, year: 2011

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).
Permanent Link: http://hdl.handle.net/11104/0198772