Organoosmium complexes of imidazole-containing chelate acceptor ligands

0349255 - ÚFCH JH 2011 RIV NL eng J - Článek v odborném periodiku
Sarper, O. - Sarkar, B. - Fiedler, Jan - Lissner, F. - Kaim, W.
Organoosmium complexes of imidazole-containing chelate acceptor ligands.
Inorganica chimica acta. Roč. 363, č. 12 (2010), s. 3070-3077. ISSN 0020-1693. E-ISSN 1873-3255
Grant CEP: GA MŠMT OC09043
Výzkumný záměr: CEZ:AV0Z40400503
Klíčová slova: arene ligand * electrochemistry * electronic structure
Kód oboru RIV: CF - Fyzikální chemie a teoretická chemie
Impakt faktor: 1.899, rok: 2010

The complexes [(L)Os(eta(6)-Cym)Cl](PF6), Cym = p-cymene and L = bis(1-methylimidazol-2-yl) ketone (bik) or bis(1-methylimidazol-2-yl) glyoxal (big), were obtained and characterized with respect to spectroscopy, crystal structure (big complex) and (spectro)electrochemical behaviour at variable temperatures. DFT calculations confirm the structure of [(big)Os(eta(6)-Cym)Cl](+) with imidazolyl-N-bonded Os-II in a boat-shaped seven-membered chelate ring with small N-Os-N angles (<84 degrees). Reduction of this compound proceeds reversibly to a neutral complex of the alpha-semidione radical anion ligand big; EPR and IR spectroelectrochemistry indicate very little participation from the heavy metal in the spin distribution. The analogous [(bik)Os(eta(6)-Cym)Cl](+) could not be reduced reversibly to the ketyl radical complex but displayed a more reversible oxidation at high potential.
Trvalý link: http://hdl.handle.net/11104/0189545