Organoosmium complexes of imidazole-containing chelate acceptor ligands
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Inorganica Chimica Acta 363 (12): 3070--3077 (2010)

(L)Os(h6-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 spectroelectrochem. behavior at variable temps. DFT calcns. confirm the structure of (big)Os(h6-Cym)Cl+ with imidazolyl-N-bonded Os(II) in a boat-shaped seven-membered chelate ring with small N-Os-N angles (\textless84°). Redn. of this compd. proceeds reversibly to a neutral complex of the a-semidione radical anion ligand big·-; EPR and IR spectroelectrochem. indicate very little participation from the heavy metal in the spin distribution. The analogous (bik)Os(h6-Cym)Cl+ could not be reduced reversibly to the ketyl radical complex but displayed a more reversible oxidn. at high potential. on SciFinder(R)
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