Electron transfer

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Example of a reduction-oxidation reaction between sodium and chlorine, with the OIL RIG mnemonic Redox example.svg
Example of a reduction–oxidation reaction between sodium and chlorine, with the OIL RIG mnemonic

Electron transfer (ET) occurs when an electron relocates from an atom, ion, or molecule, to another such chemical entity. ET describes the mechanism by which electrons are transferred in redox reactions. [2]

Contents

Electrochemical processes are ET reactions. ET reactions are relevant to photosynthesis and respiration and commonly involve transition metal complexes. [3] [4] In organic chemistry ET is a step in some industrial polymerization reactions. It is foundational to photoredox catalysis.

Classes of electron transfer

Inner-sphere electron transfer

In inner-sphere ET, 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+. [5] [6] In this case, the chloride ligand is the bridging ligand that covalently connects the redox partners. [7]

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 latter 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 route.

Outer-sphere ET reactions often occur when one/both reactants are inert or if there is no suitable bridging ligand.

A key concept of Marcus theory [8] 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 manganate.

Five steps of an outer sphere reaction

  1. Reactants diffuse together, forming an "encounter complex", 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 present in solution and the surface of a solid such as a semi-conducting material or an electrode. Theories addressing heterogeneous electron transfer have applications in electrochemistry and the design of solar cells.

Vectoral electron transfer

Especially in proteins, electron transfer often involves hopping of an electron from one redox-active center to another one. The hopping pathway, which can be viewed as a vector, guides and facilitates ET within an insulating matrix. Typical redox centers are iron-sulfur clusters, e.g. the 4Fe-4S ferredoxins. These sites are often separated by 7-10 Å, a distance compatible with fast outer-sphere ET.

Theory

The first generally accepted theory of ET was developed by Rudolph A. Marcus (Nobel Prize in Chemistry in 1992) [8] 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. [9] In proteins, ET rates are governed by the bond structures: the electrons, in effect, tunnel through the bonds comprising the chain structure of the proteins. [10]

See also

Related Research Articles

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A coordination complex is a chemical compound consisting of a central atom or ion, which is usually metallic and is called the coordination centre, and a surrounding array of bound molecules or ions, that are in turn known as ligands or complexing agents. Many metal-containing compounds, especially those that include transition metals, are coordination complexes.

<span class="mw-page-title-main">Inorganic chemistry</span> Field of chemistry

Inorganic chemistry deals with synthesis and behavior of inorganic and organometallic compounds. This field covers chemical compounds that are not carbon-based, which are the subjects of organic chemistry. The distinction between the two disciplines is far from absolute, as there is much overlap in the subdiscipline of organometallic chemistry. It has applications in every aspect of the chemical industry, including catalysis, materials science, pigments, surfactants, coatings, medications, fuels, and agriculture.

<span class="mw-page-title-main">Metallocene</span> Type of compound having a metal center

A metallocene is a compound typically consisting of two cyclopentadienyl anions (C
5
H
5
, abbreviated Cp) bound to a metal center (M) in the oxidation state II, with the resulting general formula (C5H5)2M. Closely related to the metallocenes are the metallocene derivatives, e.g. titanocene dichloride or vanadocene dichloride. Certain metallocenes and their derivatives exhibit catalytic properties, although metallocenes are rarely used industrially. Cationic group 4 metallocene derivatives related to [Cp2ZrCH3]+ catalyze olefin polymerization.

<span class="mw-page-title-main">Oxidizing agent</span> Chemical compound used to oxidize another substance in a chemical reaction

An oxidizing agent is a substance in a redox chemical reaction that gains or "accepts"/"receives" an electron from a reducing agent. In other words, an oxidizer is any substance that oxidizes another substance. The oxidation state, which describes the degree of loss of electrons, of the oxidizer decreases while that of the reductant increases; this is expressed by saying that oxidizers "undergo reduction" and "are reduced" while reducers "undergo oxidation" and "are oxidized". Common oxidizing agents are oxygen, hydrogen peroxide, and the halogens.

<span class="mw-page-title-main">Potassium permanganate</span> Chemical compound

Potassium permanganate is an inorganic compound with the chemical formula KMnO4. It is a purplish-black crystalline salt, that dissolves in water as K+ and MnO
4
, an intensely pink to purple solution.

<span class="mw-page-title-main">Henry Taube</span> Canadian-born American chemist (1915–2005)

Henry Taube was a Canadian-born American chemist who was awarded the 1983 Nobel Prize in Chemistry for "his work in the mechanisms of electron-transfer reactions, especially in metal complexes." He was the second Canadian-born chemist to win the Nobel Prize, and remains the only Saskatchewanian-born Nobel laureate. Taube completed his undergraduate and master's degrees at the University of Saskatchewan, and his PhD from the University of California, Berkeley. After finishing graduate school, Taube worked at Cornell University, the University of Chicago and Stanford University.

<span class="mw-page-title-main">Permanganate</span> Chemical compound

A permanganate is a chemical compound with the manganate(VII) ion, MnO
4
, the conjugate base of permanganic acid. Because the manganese atom has a +7 oxidation state, the permanganate(VII) ion is a strong oxidising agent. The ion is a transition metal ion with a tetrahedral structure. Permanganate solutions are purple in colour and are stable in neutral or slightly alkaline media. The exact chemical reaction depends on the carbon-containing reactants present and the oxidant used. For example, trichloroethane (C2H3Cl3) is oxidised by permanganate ions to form carbon dioxide (CO2), manganese dioxide (MnO2), hydrogen ions (H+), and chloride ions (Cl).

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<span class="mw-page-title-main">Potassium manganate</span> Chemical compound

Potassium manganate is the inorganic compound with the formula K2MnO4. This green-colored salt is an intermediate in the industrial synthesis of potassium permanganate, a common chemical. Occasionally, potassium manganate and potassium permanganate are confused, but each compound's properties are distinct.

Inner sphere electron transfer 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, inner sphere 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.

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. In contrast, for inner sphere electron transfer the participating redox sites undergoing ET become connected by a chemical bridge. Because the ET in outer sphere electron transfer occurs between two non-connected species, the electron is forced to move through space from one redox center to the other.

In theoretical chemistry, Marcus theory is a theory originally developed by Rudolph A. Marcus, starting in 1956, to explain the rates of electron transfer reactions – the rate at which an electron can move or jump from one chemical species (called the electron donor) to another (called the electron acceptor). It was originally formulated to address outer sphere electron transfer reactions, in which the two chemical species only change in their charge with an electron jumping (e.g. the oxidation of an ion like Fe2+/Fe3+), but do not undergo large structural changes. It was extended to include inner sphere electron transfer contributions, in which a change of distances or geometry in the solvation or coordination shells of the two chemical species is taken into account (the Fe-O distances in Fe(H2O)2+ and Fe(H2O)3+ are different).

Potassium hypomanganate is the inorganic compound with the formula K3MnO4. Also known as potassium manganate(V), this bright blue solid is a rare example of a salt with the hypomanganate or manganate(V) anion, where the manganese atom is in the +5 oxidation state. It is an intermediate in the production of potassium permanganate and the industrially most important Mn(V) compound.

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