%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 }