Analysis of Multiple Redox Sites in Complexes [M(Cinf5/infMeinf5/inf)(Q)(NO)]supn/sup, M=Ru or Os, Q=o-Quinones

0541686 - ÚFCH JH 2022 RIV DE eng J - Journal Article
Scherer, T. M. - Hartenbach, I. - Lissner, F. - Schwederski, B. - Hübner, R. - Fiedler, Jan - Záliš, Stanislav - Sarkar, B. - Kaim, W.
Analysis of Multiple Redox Sites in Complexes [M(Cinf5/infMeinf5/inf)(Q)(NO)]supn/sup, M=Ru or Os, Q=o-Quinones.
Zeitschrift für anorganische und allgemeine Chemie. Roč. 647, č. 8 (2021), s. 867-875. ISSN 0044-2313. E-ISSN 1521-3749
Institutional support: RVO:61388955
Keywords : Nitrosyl complexes * Osmium compounds * Redox systems * Ruthenium compounds * Spectroelectrochemistry
OECD category: Physical chemistry
Impact factor: 1.414, year: 2021
Method of publishing: Open access

Neutral complexes [M-II(C5Me5)(Q(2-))(NO+)] with M=Ru or Os and the catecholates Q(2-) with 3,5-di-tert-butyl (dtbc) or 3,4,5,6-tetrachloro substituents (tcc) were identified with the oxidation and charge states indicated. Reversible electron transfer was analyzed spectroelectrochemically (EPR, UV-vis-NIR, IR), supported by DFT calculations. Reversible reduction was observed for [Ru(C5Me5)(tcc)(NO)] to occur on the nitrosyl ligand to yield the NO radical complex [Ru-II(C5Me5)(tcc(2-))(NO.)](-), whereas the stepwise oxidation yielded o-semiquinone cations, [M-II(C5Me5)(Q(.-))(NO+)](+), and dications. The metals remained in the stable low-spin d(6) states, Ru-II and Os-II, respectively. Redox potentials were found to depend strongly on the donor or acceptor substitution pattern at Q(n).
Permanent Link: http://hdl.handle.net/11104/0319214