Electron transfer and chloride ligand dissociation in complexes [(C5Me5)ClM(bpy)]+/[(C5Me5)M(bpy)]n (M = Co, Rh, Ir; n = 2+, +, 0, -): A combined electrochemical and spectroscopic investigation
In contrast to the rapid and chem. reversible two-electron ECE' reductive elimination reaction [(C5Me5)ClM(bpy)]+ + 2e-$\rightarrow$(C5Me5)M(bpy) + Cl-, M = Rh or Ir, the analogous cobalt system exhibits two sep. one-electron steps (EC + E' process) with a persistent, EPR-spectroscopically characterized cobalt(II) intermediate [(C5Me5)Co(bpy)]+. Within the series of coordinatively unsatd. homologous species (C5Me5)M(bpy), the cobalt deriv. exhibits the smallest and the iridium homolog the largest metal(I)-to-bpy electron transfer in the ground state, as evident from electrochem. potentials and long-wavelength absorption data. A comparison within that homologous series indicates why the rhodium system, with its intermediate position, is most suitable for hydride transfer catalysis. [on SciFinder(R)]
%0 Journal Article
%1 Kaim.1996
%A Kaim, Wolfgang
%A Reinhardt, Ralf
%A Waldhoer, Eberhard
%A Fiedler, Jan.
%D 1996
%J Journal of Organometallic Chemistry
%K bipyridine;reductive bpy chloride chloride;electrochem chloride;electron cobalt cyclopentadienylcobalt;ESR dissocn elimination iridium ligand pentamethylcyclopentadienyl pentamethylcyclopentadienylcobalt potential rhodium transfer
%N 1-2
%P 195--202
%R 10.1016/S0022-328X(96)06426-1
%T Electron transfer and chloride ligand dissociation in complexes [(C5Me5)ClM(bpy)]+/[(C5Me5)M(bpy)]n (M = Co, Rh, Ir; n = 2+, +, 0, -): A combined electrochemical and spectroscopic investigation
%V 524
%X In contrast to the rapid and chem. reversible two-electron ECE' reductive elimination reaction [(C5Me5)ClM(bpy)]+ + 2e-$\rightarrow$(C5Me5)M(bpy) + Cl-, M = Rh or Ir, the analogous cobalt system exhibits two sep. one-electron steps (EC + E' process) with a persistent, EPR-spectroscopically characterized cobalt(II) intermediate [(C5Me5)Co(bpy)]+. Within the series of coordinatively unsatd. homologous species (C5Me5)M(bpy), the cobalt deriv. exhibits the smallest and the iridium homolog the largest metal(I)-to-bpy electron transfer in the ground state, as evident from electrochem. potentials and long-wavelength absorption data. A comparison within that homologous series indicates why the rhodium system, with its intermediate position, is most suitable for hydride transfer catalysis. [on SciFinder(R)]
@article{Kaim.1996,
abstract = {In contrast to the rapid and chem. reversible two-electron ECE' reductive elimination reaction [(C5Me5)ClM(bpy)]+ + 2e-$\rightarrow$(C5Me5)M(bpy) + Cl-, M = Rh or Ir, the analogous cobalt system exhibits two sep. one-electron steps (EC + E' process) with a persistent, EPR-spectroscopically characterized cobalt(II) intermediate [(C5Me5)Co(bpy)]+. Within the series of coordinatively unsatd. homologous species (C5Me5)M(bpy), the cobalt deriv. exhibits the smallest and the iridium homolog the largest metal(I)-to-bpy electron transfer in the ground state, as evident from electrochem. potentials and long-wavelength absorption data. A comparison within that homologous series indicates why the rhodium system, with its intermediate position, is most suitable for hydride transfer catalysis. [on SciFinder(R)]},
added-at = {2022-06-15T11:26:56.000+0200},
author = {Kaim, Wolfgang and Reinhardt, Ralf and Waldhoer, Eberhard and Fiedler, Jan.},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/254d4bb1bc54b7ae36da5e950dc0a284b/huebleriac},
doi = {10.1016/S0022-328X(96)06426-1},
interhash = {48440717270f5974c49d54b8a1de9fdc},
intrahash = {54d4bb1bc54b7ae36da5e950dc0a284b},
journal = {Journal of Organometallic Chemistry},
keywords = {bipyridine;reductive bpy chloride chloride;electrochem chloride;electron cobalt cyclopentadienylcobalt;ESR dissocn elimination iridium ligand pentamethylcyclopentadienyl pentamethylcyclopentadienylcobalt potential rhodium transfer},
number = {1-2},
pages = {195--202},
timestamp = {2022-06-15T09:26:56.000+0200},
title = {Electron transfer and chloride ligand dissociation in complexes [(C5Me5)ClM(bpy)]+/[(C5Me5)M(bpy)]n (M = Co, Rh, Ir; n = 2+, +, 0, -): A combined electrochemical and spectroscopic investigation},
volume = 524,
year = 1996
}
