Inner Sphere And Outer Sphere Mechanism Pdf
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The extremely large surface areas as well as connecting nanopores of single-walled carbon nanohorn SWCNH aggregates have been tested, for the first time to the best of our knowledge, as metal-free, stable and cheap electrocatalysts for heterogeneous electron transfer reactions involving inorganic redox couples, including f-block elements such as actinides. It was evident that the oxygen containing functional groups of o-SWCNH could catalyze the electron transfer process between uranium species in solution and the working electrode happened by following surface-sensitive inner-sphere electron transfer mechanism.
Outer sphere refers to an electron transfer ET event that occurs between chemical species that remain separate and intact before, during, and after the ET event.
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Inner sphere electron transfer
Inner sphere electron transfer IS ET or bonded electron transfer  is a redox chemical reaction that proceeds via a covalent linkage—a strong electronic interaction—between the oxidant and the reductant reactants. In inner sphere electron transfer, a ligand bridges the two metal redox centers during the electron transfer event. Inner sphere reactions are inhibited by large ligands, which prevent the formation of the crucial bridged intermediate. Thus, IS ET is rare in biological systems, where redox sites are often shielded by bulky proteins. Inner sphere ET is usually used to describe reactions involving transition metal complexes and most of this article is written from this perspective. However, redox centers can consist of organic groups rather than metal centers.
In some cases, electron transfers occur much more quickly in the presence of certain ligands. For example, compare the rate constants for the following two electron transfer reactions, involving almost exactly the same complexes:. Note: aqua ligands are omitted for simplicity. Ions, unless noted otherwise, are aqua complexes. Notice two things: first, when there is a chloride ligand involved, the reaction is much faster.
1.10: Inner Sphere Electron Transfer
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