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electron-transfer catalysis

The term indicates a sequence of reactions such as shown in equations (1)–(3), leading from A to B :
A + e − → A · −
A · − → B · −
B · − + A → B + A · −
An analogous sequence involving radical cations (A+., B+.) is also observed. The most notable example of electron-transfer catalysis is the S RN 1 (or T + D N + A N) reaction of aromatic halides. The term has its origin in a suggested analogy to acid-base catalysis, with the electron instead of the proton. However, there is a difference between the two catalytic mechanisms, since the electron is not a true catalyst, but rather behaves as the initiator of a chain reaction. 'Electron-transfer induced chain reaction' is a more appropriate term for the situation described by equations (1)–(3).
PAC, 1994, 66, 1077 (Glossary of terms used in physical organic chemistry (IUPAC Recommendations 1994)) on page 1110
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IUPAC. Compendium of Chemical Terminology, 2nd ed. (the "Gold Book"). Compiled by A. D. McNaught and A. Wilkinson. Blackwell Scientific Publications, Oxford (1997). XML on-line corrected version: (2006-) created by M. Nic, J. Jirat, B. Kosata; updates compiled by A. Jenkins. ISBN 0-9678550-9-8.
Last update: 2014-02-24; version: 2.3.3.
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