Electron transfer

From Wikipedia, the free encyclopedia

Jump to navigation Jump to search

Electron transfer (ET) occurs when an electron relocates from an atom or molecule to
another such chemical entity. ET is a mechanistic description of a redox reaction, wherein the
oxidation state of reactant and product changes. Electron transfer is ionic bonding.

Numerous biological processes involve ET reactions. These processes include oxygen

binding, photosynthesis, respiration, and detoxification. Additionally, the process of energy
transfer can be formalized as a two-electron exchange (two concurrent ET events in opposite
directions) in case of small distances between the transferring molecules. ET reactions
commonly involve transition metal complexes,[1][2] but there are now many examples of ET
in organic chemistry.

Contents
 1 Classes of electron transfer
o 1.1 Inner-sphere electron transfer
o 1.2 Outer-sphere electron transfer
 1.2.1 Five steps of an outer sphere reaction
o 1.3 Heterogeneous electron transfer
 2 Theory
 3 See also
 4 References

Classes of electron transfer

There are several classes of electron transfer, defined by the state of the two redox centers
and their connectivity

Inner-sphere electron transfer

Main article: Inner-sphere electron transfer

In inner-sphere ET, the two redox centers are covalently linked during the ET. This bridge
can be permanent, in which case the electron transfer event is termed intramolecular electron
transfer. More commonly, however, the covalent linkage is transitory, forming just prior to
the ET and then disconnecting following the ET event. In such cases, the electron transfer is
termed intermolecular electron transfer. A famous example of an inner sphere ET process that
proceeds via a transitory bridged intermediate is the reduction of [CoCl(NH3)5]2+ by
[Cr(H2O)6]2+. In this case the chloride ligand is the bridging ligand that covalently connects
the redox partners.

Outer-sphere electron transfer

Main article: Outer-sphere electron transfer

In outer-sphere ET reactions, the participating redox centers are not linked via any bridge
during the ET event. Instead, the electron "hops" through space from the reducing center to
the acceptor. Outer sphere electron transfer can occur between different chemical species or
between identical chemical species that differ only in their oxidation state. The later process
is termed self-exchange. As an example, self-exchange describes the degenerate reaction
between permanganate and its one-electron reduced relative manganate:

[MnO4]− + [Mn*O4]2− → [MnO4]2− + [Mn*O4]−

In general, if electron transfer is faster than ligand substitution, the reaction will follow the
outer-sphere electron transfer.

Often occurs when one/both reactants are inert or if there is no suitable bridging ligand.

A key concept of Marcus theory is that the rates of such self-exchange reactions are
mathematically related to the rates of "cross reactions". Cross reactions entail partners that
differ by more than their oxidation states. One example (of many thousands) is the reduction
of permanganate by iodide to form iodine and, again, manganate.

Five steps of an outer sphere reaction

 1. reactants diffuse together out of their solvent shells => precursor complex (requires
work =wr)
 2. changing bond lengths, reorganize solvent => activated complex
 3. Electron transfer
 4. Relaxation of bond lengths, solvent molecules => successor complex
 5. Diffusion of products (requires work=wp)

Heterogeneous electron transfer

In heterogeneous electron transfer, an electron moves between a chemical species and a solid-
state electrode. Theories addressing heterogeneous electron transfer have applications in
electrochemistry and the design of solar cells.

Theory
The first generally accepted theory of ET was developed by Rudolph A. Marcus to address
outer-sphere electron transfer and was based on a transition-state theory approach. The
Marcus theory of electron transfer was then extended to include inner-sphere electron transfer
by Noel Hush and Marcus. The resultant theory, called Marcus-Hush theory, has guided most
discussions of electron transfer ever since. Both theories are, however, semiclassical in
nature, although they have been extended to fully quantum mechanical treatments by Joshua
Jortner, Alexander M. Kuznetsov, and others proceeding from Fermi's Golden Rule and
following earlier work in non-radiative transitions. Furthermore, theories have been put
forward to take into account the effects of vibronic coupling on electron transfer; in
particular, the PKS theory of electron transfer.[3]
Before 1991, ET in metalloproteins was thought to affect primarily the diffuse, averaged
properties of the non-metal atoms forming an insulated barrier between the metals, but
Beratan, Betts and Onuchic [4] subsequently showed that the ET rates are governed by the
bond structures of the proteins -- that the electrons, in effect, tunnel through the bonds
comprising the chain structure of the proteins.

See also
 Electron equivalent
 Electrochemical reaction mechanism
 Solvated electron