Kinetic solvent effects on hydrogen abstraction reactions.
Kinetic solvent effects on hydrogen abstractions, namely, acceleration in nonpolar solvents, have been presumed to be restricted to O-H hydrogen donors. We demonstrate that also abstractions from C-H and even Sn-H bonds by cumyloxyl radicals and n,pi*-excited 2,3-diazabicyclo[2.2.2]oct-2-ene are fastest in the gas phase and nonpolar solvents but slowest in acetonitrile. Accordingly, solvent effects on hydrogen abstractions are more general, presumably due to stabilization of the reactive oxygen or nitrogen species in polar solvents.
Koner
Apurba L
AL
School of Engineering and Science, Jacobs University Bremen, Campus Ring 1, D-28759 Bremen, Germany.
Pischel
Uwe
U
Nau
Werner M
WM