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Organoosmium complexes of imidazole-containing chelate acceptor ligands
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SYSNO ASEP 0349255 Document Type J - Journal Article R&D Document Type Journal Article Subsidiary J Článek ve WOS Title Organoosmium complexes of imidazole-containing chelate acceptor ligands Author(s) Sarper, O. (DE)
Sarkar, B. (DE)
Fiedler, Jan (UFCH-W) RID, ORCID
Lissner, F. (DE)
Kaim, W. (DE)Source Title Inorganica chimica acta. - : Elsevier - ISSN 0020-1693
Roč. 363, č. 12 (2010), s. 3070-3077Number of pages 8 s. Language eng - English Country NL - Netherlands Keywords arene ligand ; electrochemistry ; electronic structure Subject RIV CF - Physical ; Theoretical Chemistry R&D Projects OC09043 GA MŠMT - Ministry of Education, Youth and Sports (MEYS) CEZ AV0Z40400503 - UFCH-W (2005-2011) UT WOS 000282360200051 DOI 10.1016/j.ica.2010.04.007 Annotation 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. Workplace J. Heyrovsky Institute of Physical Chemistry Contact Michaela Knapová, michaela.knapova@jh-inst.cas.cz, Tel.: 266 053 196 Year of Publishing 2011
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