Outer Sphere Electron Transfer
Redox reactions are preferably run in polar solvents. Donor and acceptor then have a solvent shell and the precursor and successor complexes are solvated also. The closest molecules of the solvent shell, or the ligands in complexes, are tightly bound and constitute the "inner sphere". Reactions in which these participate are called inner sphere redox reactions. The free solvent molecules constitute the "outer sphere". Outer sphere redox reactions do not change the inner sphere, no bonds are made nor broken.
It was R.A. Marcus who realized the role of the solvent when he worked on the nature and magnitude of the Gibbs free energy of activation for redox reactions, more precisely: one-electron transfer reactions of the outer sphere type. He published two fundamental papers. The ideas of these two papers are often referred to Marcus Theory although Marcus’ later work goes much beyond them. In the following the development and results of the ideas of these two papers are outlined. For the mathematics and more details the original papers should be consulted.
Read more about this topic: Marcus Theory
Famous quotes containing the words outer, sphere and/or transfer:
“No one knows better than children how much they need the authority that protects, that sets the outer limits of behavior with known and prescribed consequences. As one little boy expressed it to his mother, “You care what I do.””
—Leontine Young (20th century)
“No person can be considered as possessing a good education without religion. A good education is that which prepares us for our future sphere of action and makes us contented with that situation in life in which God, in his infinite mercy, has seen fit to place us, to be perfectly resigned to our lot in life, whatever it may be.”
—Ann Plato (1820–?)
“If it had not been for storytelling, the black family would not have survived. It was the responsibility of the Uncle Remus types to transfer philosophies, attitudes, values, and advice, by way of storytelling using creatures in the woods as symbols.”
—Jackie Torrence (b. 1944)