Oxidation State Analysis of a Four-Component Redox Series [Os(pap)2(Q)]n Involving Two Different Non-Innocent Ligands on a Redox-Active Transition Metal

0363080 - ÚFCH JH 2012 RIV US eng J - Článek v odborném periodiku
Das, D. - Sarkar, B. - Mondal, T. K. - Mobin, S. M. - Fiedler, Jan - Kaim, W. - Lahiri, G. K.
Oxidation State Analysis of a Four-Component Redox Series [Os(pap)2(Q)]n Involving Two Different Non-Innocent Ligands on a Redox-Active Transition Metal.
Inorganic Chemistry. Roč. 50, č. 15 (2011), s. 7090-7098. ISSN 0020-1669. E-ISSN 1520-510X
Grant CEP: GA ČR GA203/09/0705; GA MŠMT LD11086
Výzkumný záměr: CEZ:AV0Z40400503
Klíčová slova: oxidation state analysis * [Os(pap)2(Q)]n * redox-active transition metal
Kód oboru RIV: CF - Fyzikální chemie a teoretická chemie
Impakt faktor: 4.601, rok: 2011

Complexes [Os(pap)2(Q)] (1–4) have been obtained and structurally characterized for pap = 2-phenylazopyridine and Q = 4,6-di-tert-butyl-N-aryl-o-iminobenzoquinone (aryl = phenyl (1), 3,5-dichlorophenyl (2), 3,5-dimethoxyphenyl (3), or 3,5-di-tert-butylphenyl (4)). The oxidized form (3)(ClO4)2 was also crystallographically characterized while the odd-electron intermediates [Os(pap)2(Q)]+ (1+–4+) and [Os(pap)2(Q)]− (2–) were investigated by electron paramagnetic resonance (EPR) and UV–vis–NIR spectroelectrochemistry in conjunction with density functional theory (DFT) spin density and time-dependent DFT (TD-DFT) calculations. The results from the structural, spectroscopic, and electrochemical experiments and from the computational studies allow for the assignments [OsII(pap0)2(Q0)]2+, [OsII(pap0)2(Q•–)]+, [OsIV(pap•–)2(Q2–)], and [OsII(pap•–)(pap0)(Q2–)]−, with comproportionation constants Kc ≈ 103.5, 1010, 1018, and 105, respectively.
Trvalý link: http://hdl.handle.net/11104/0006525