Inner Sphere Electron Transfer - Taube's Experiment

Taube's Experiment

The discoverer of the inner sphere mechanism was Henry Taube, who was awarded the Nobel Prize in Chemistry in 1983 for his pioneering studies. A particularly historic finding is summarized in the abstract of the seminal publication. “When Co(NH₃)₅Cl++ is reduced by Cr++ in M {meaning 1M} HClO₄, 1 Cl− appears attached to Cr for each Cr(III) which is formed or Co(III) reduced. When the reaction is carried on in a medium containing radioactive Cl, the mixing of the Cl− attached to Cr(III) with that in solution is less than 0.5%. This experiment shows that transfer of Cl to the reducing agent from the oxidizing agent is direct…” The paper and the excerpt above can be described with the following equation:

2+ + 2+ → 2+ + 2+

The point of interest is that the chloride that was originally bonded to the cobalt, the oxidant, becomes bonded to chromium, which in its +3 oxidation state, forms kinetically inert bonds to its ligands. This observation implies the intermediacy of the bimetallic complex 4+, wherein "μ-Cl" indicates that the chloride bridges between the Cr and Co atoms, serving as a ligand for both. This chloride serves as a conduit for electron flow from Cr(II) to Co(III), forming Cr(III) and Co(II).