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Organoosmium complexes of imidazole-containing chelate acceptor ligands
- 1.0349255 - ÚFCH JH 2011 RIV NL eng J - Journal Article
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
R&D Projects: GA MŠMT OC09043
Institutional research plan: CEZ:AV0Z40400503
Keywords : arene ligand * electrochemistry * electronic structure
Subject RIV: CF - Physical ; Theoretical Chemistry
Impact factor: 1.899, year: 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.
Permanent Link: http://hdl.handle.net/11104/0189545
Number of the records: 1