Coupling of electron transfer and bond dissociation processes in dinuclear complexes with rhodium and iridium reaction centres bridged by 2,2'-bipyrimidine
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Collection of Czechoslovak Chemical Communications 66 (2): 291--306 (2001)

The complexes MCl(η5-C5Me5)2(m-bpym)(PF6)2, bpym = 2,2'-bipyrimidine and M = Rh or Ir, were obtained as isomerically pure species (M = Ir) or as mixts. of cis/trans isomers (M = Rh). Even though these compds. undergo partial dissocn. into the mononuclear bpym- and solvento-complexes in DMF or acetonitrile, cyclic voltammetry and, in part, spectroscopy (NMR, EPR, UV-VIS) could be used to analyze their redn. with up to five electrons. In acetonitrile at room temp., the dirhodium compd. displays two sequential chloride-dissociative two-electron cathodic steps, leading to the very reactive Rh(η5-C5Me5)2(m-bpym). At -15° in DMF, the diiridium compd. was found to be sufficiently inert towards dissocn.; it is then reversibly reduced to an EPR-detectable radical cation IrCl(η5-C5Me5)2(m-bpym)·+ before two sepd. chloride-dissociative steps occur. on SciFinder(R)
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