Structure and Spectroelectrochemical Response of Arene-Ruthenium and Arene-Osmium Complexes with Potentially Hemilabile Noninnocent Ligands

0433935 - ÚFCH JH 2015 RIV US eng J - Journal Article
Bubrin, M. - Schweinfurth, D. - Ehret, F. - Záliš, Stanislav - Kvapilová, Hana - Fiedler, Jan - Zeng, Q. - Hartl, F. - Kaim, W.
Structure and Spectroelectrochemical Response of Arene-Ruthenium and Arene-Osmium Complexes with Potentially Hemilabile Noninnocent Ligands.
Organometallics. Roč. 33, č. 18 (2014), s. 4973-4985. ISSN 0276-7333. E-ISSN 1520-6041
R&D Projects: GA MŠMT LD14129
Grant - others:COST(XE) cm1202
Institutional support: RVO:61388955
Keywords : TRANSITION-METAL-COMPLEXES * REDOX-ACTIVE LIGANDS * TRANSFER HYDROGENATION
Subject RIV: CG - Electrochemistry
Impact factor: 4.126, year: 2014

Nine of the compounds [M(L2-)(p-cymene)] (M = Ru, Os, L2- = 4,6-di-tert-butyl-N-aryl-o-amidophenolate) were prepared and structurally characterized (Ru complexes) as coordinatively unsaturated, formally 16 valence electron species. On L2--ligand based oxidation to EPR-active itninosemiquinone radical complexes, the compounds seek to bind a donor atom (if available) from the N-aryl substituent, as structurally certified for thioether and selenoether functions, or from the donor solvent. Simulated cyclic voltammograms and spectroelectrochemistry at ambient and low temperatures in combination with DFT results confirm a square scheme behavior (ECEC mechanism) involving the L-n ligand ligand. as the main electron transfer site and the metal with fractional (delta) oxidation as the center for redox-activated coordination. Attempts to crystallize [Ru(Cym)(Q(SMe))](PF6) produced single crystals of [Ru-III(Q(SMe)(center dot-))(2)](PF6) after apparent dissociation of the arene ligand.
Permanent Link: http://hdl.handle.net/11104/0238102