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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.
A Proton-coupled electron transfer (PCET) is a chemical reaction that involves the transfer of electrons and protons from one atom to another. The term was originally coined for single proton, single electron processes that are concerted, [1] but the definition has relaxed to include many related processes.
In outer sphere redox reactions no bonds are formed or broken; only an electron transfer (ET) takes place. A quite simple example is the Fe 2+ /Fe 3+ redox reaction, the self exchange reaction which is known to be always occurring in an aqueous solution containing the aquo complexes [Fe(H 2 O) 6] 2+ and [Fe(H 2 O)6] 3+.
Outer sphere electron transfer can occur between chemical species that are identical except for their oxidation state. [4] This process is termed self-exchange. An example is the degenerate reaction between the tetrahedral ions permanganate and manganate:
The mechanism of reductions of aldehydes and ketones by samarium(II) iodide is based primarily on mechanisms elucidated for similar one-electron reducing agents. [12] Upon single-electron transfer, a ketyl dimer iv forms. In the absence of protic solvent, this dimer collapses to form 1,2-diols.
[40] [41] These reactions use Umemoto's reagent, a sulfonium salt that serves as an electrophilic source of the trifluoromethyl group and that is precedented to react via a single-electron transfer pathway. Thus, single-electron reduction of Umemoto's reagent releases trifluoromethyl radical, which adds to the reactive olefin. Subsequently ...
Electrochemical mechanisms are important to all redox chemistry including corrosion, redox active photochemistry including photosynthesis, other biological systems often involving electron transport chains and other forms of homogeneous and heterogeneous electron transfer. Such reactions are most often studied with standard three electrode ...
The radical mechanism of the Sandmeyer reaction is supported by the detection of biaryl byproducts. [8] The substitution of the aromatic diazo group with a halogen or pseudohalogen is initiated by a one-electron transfer mechanism catalyzed by copper(I) to form an aryl radical with loss of nitrogen gas.