Bis(acetylacetonato)ruthenium Complexes of Noninnocent 1,2-Dioxolene Ligands: Qualitatively Different Bonding in Relation to Monoimino and Diimino Analogues

0369092 - ÚFCH JH 2012 RIV DE eng J - Článek v odborném periodiku
Das, D. - Sarkar, B. - Kumbhakar, D. - Mondal, T. P. - Mobin, S. M. - Fiedler, Jan - Urbanos, F. A. - Jimenez-Aparicio, R. - Kaim, W. - Lahiri, G. K.
Bis(acetylacetonato)ruthenium Complexes of Noninnocent 1,2-Dioxolene Ligands: Qualitatively Different Bonding in Relation to Monoimino and Diimino Analogues.
Chemistry - A European Journal. Roč. 17, č. 39 (2011), s. 11030-11040. ISSN 0947-6539. E-ISSN 1521-3765
Grant CEP: GA ČR GA203/09/0705; GA MŠMT(CZ) LD11082
Výzkumný záměr: CEZ:AV0Z40400503
Klíčová slova: density functional calculations * magnetic properties * ruthenium
Kód oboru RIV: CF - Fyzikální chemie a teoretická chemie
Impakt faktor: 5.925, rok: 2011

Coordination compounds [Ru(acac)(2)(Q)] (acac = acetylacetonate; Q = o-benzoquinone) were prepared as complexes 1 (Q = o-benzoquinone), 2 (Q = 3-methoxy-o-benzoquinone), 3 (Q = 4-methyl-o-benzoquinone), and 4 (Q = 3,5-di-tert-butyl-o-benzoquinone). The structures of 1 and 2 were determined to reveal a Ru(III)/o-benzosemiquinone formulation, supported by analysis of experimental data (spectroscopy, magnetism of 1) and by DFT calculations. The S = 1 ground state calculated for 1 stands in contrast to the spin-paired analogues with arylimino-o-benzosemiquinonato and diimino-o-benzoquinone ligands. The close contacts of about 5.3 angstrom possible between semiquinone O atoms of different molecules in the crystal allow for intermolecular spin-spin interactions and an overall complex magnetic behavior. One quasireversible oxidation and two reversible one-electron reductions yielded the corresponding molecular ions, which were characterized by UV-visible-NIR and EPR spectroelectrochemistry in terms of [Ru(III)(acac)(2)(Q(0))](+), [Ru(III)(acac)(2)(Q(2-))](-), and [Ru(II)(acac)(2)(Q(2-))](2-) descriptions in agreement with DFT results.
Trvalý link: http://hdl.handle.net/11104/0203241