Cyclopropylcarbinyl --> homoallyl-type ring opening of ketyl radical anions. Structure/reactivity relationships and the contribution of solvent/counterion reorganization to the intrinsic barrier.

[reaction: see text] Following a protocol developed by Mathivanan, Johnston, and Wayner (J. Phys. Chem.

Chemistry of the t-butoxyl radical: evidence that most hydrogen abstractions from carbon are entropy-controlled.

Absolute rate constants and Arrhenius parameters for hydrogen abstractions (from carbon) by the t-butoxyl radical ((t) BuO.) are reported for several hydrocarbons and tertiary amines in solution. Combined with data already in the literature, an analysis of all the available data reveals that most hydrogen abstractions (from carbon) by (t) BuO.