Abstract
In contrast to the rapid and chemically reversible two-electron ECE′ reductive elimination reaction[(C 5Me 5)ClM(bpy)] + + 2e − → (C 5Me 5)M(bpy)+Cl −,M=Rh or Ir, the analogous cobalt system exhibits two separate one-electron steps (EC + E′ process) with a persistent, EPR-spectroscopically characterized cobalt(II) intermediate [(C 5Me 5)Co(bpy)] +. Within the series of coordinatively unsaturated homologous species (C 5Me 5)M(bpy), the cobalt derivative exhibits the smallest and the iridium homologue the largest metal(I)-to-bpy electron transfer in the ground state, as evident from electrochemical 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.
Published Version
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