Intramolecular long-distance electron transfer in radical anions. The effects of free energy and solvent on the reaction rates

Journal Article · Wed May 16 00:00:00 EDT 1984 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00322a058· OSTI ID:6681120

Miller, J R; Calcaterra, L T; Closs, G L

A homologous series of eight compounds of the general structure A-Sp-B where B is 4-biphenylyl, Sp is a rigid saturated hydrocarbon spacer, the steroidal 5..cap alpha..-androstane skeleton, and A is one of a series of 8 different molecular groups with ..pi.. electron networks was synthesized. A liquid solution of these molecules in either 2-methyltetrahydrofuran or isooctane at room temperature was subjected to a 30-ps pulse of solvated electrons. Data are presented that demonstrate in these systems the dependence of the electron transfer rates on the exothermicity of the reaction and on solvent polarity. It is also noted that the electron transfer reactions are free ion reactions.

• Research Organization: Argonne National Lab., IL
• DOE Contract Number: W-31-109-ENG-38
• OSTI ID: 6681120
• Journal Information: J. Am. Chem. Soc.; (United States), Vol. 106:10
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
74 ATOMIC AND MOLECULAR PHYSICS
ANIONS
ELECTRON TRANSFER
AROMATICS
CHEMICAL REACTION KINETICS
SOLVATED ELECTRONS
EXPERIMENTAL DATA
MTHF
OCTANE
ALKANES
CHARGED PARTICLES
DATA
ELECTRONS
ELEMENTARY PARTICLES
FERMIONS
FURANS
HETEROCYCLIC COMPOUNDS
HYDROCARBONS
INFORMATION
IONS
KINETICS
LEPTONS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
REACTION KINETICS
TETRAHYDROFURAN
400600* - Radiation Chemistry
640304 - Atomic
Molecular & Chemical Physics- Collision Phenomena