Coupling of electron transfer and bond dissociation processes in dinuclear complexes with rhodium and iridium reaction centres bridged by 2,2'-bipyrimidine
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)
%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
}
