%0 Journal Article %1 Kaim.2001c %A Kaim, Wolfgang %A Reinhardt, Ralf %A Greulich, Stefan %A Sieger, Monika %A Klein, Axel %A Fiedler, Jan. %D 2001 %J Collection of Czechoslovak Chemical Communications %K bipyrimidine complex cyclopentadienyl electrochem electrochem;rhodium iridium prepn %N 2 %P 291--306 %R 10.1135/cccc20010291 %T Coupling of electron transfer and bond dissociation processes in dinuclear complexes with rhodium and iridium reaction centres bridged by 2,2'-bipyrimidine %V 66 %X 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)]

@article{Kaim.2001c, abstract = {The complexes [{MCl(η5-C5Me5)}2(\textgreek{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(\textgreek{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(\textgreek{m}-bpym)]·+ before two sepd. chloride-dissociative steps occur. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Kaim, Wolfgang and Reinhardt, Ralf and Greulich, Stefan and Sieger, Monika and Klein, Axel and Fiedler, Jan.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2dd248c124ebc8df1dec1a75aa6eb22d2/huebleriac}, doi = {10.1135/cccc20010291}, interhash = {f2c7b7cde7fa75b4e7cbb09f94e70b2f}, intrahash = {dd248c124ebc8df1dec1a75aa6eb22d2}, issn = {0010-0765}, journal = {Collection of Czechoslovak Chemical Communications}, keywords = {bipyrimidine complex cyclopentadienyl electrochem electrochem;rhodium iridium prepn}, number = 2, pages = {291--306}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {Coupling of electron transfer and bond dissociation processes in dinuclear complexes with rhodium and iridium reaction centres bridged by 2,2'-bipyrimidine}, volume = 66, year = 2001 }