Abstract
a-Deuterium kinetic isotope effects (KIE's) have been determined
for the reaction of methyl iodide with a series of reducing
agents. Reagents which transfer hydride ion in an SN2 reaction
show small inverse or small normal KIE's. Reagents which transfer
an electron to methyl iodide to produce methyl radical show large
normal KIE's up to 20 % per a-D. Large KIE's were found for the
reaction of methyl iodide with sodium, for Pd-catalyzed reaction
of methyl iodide with hydrogen, for ET at a platinum cathode, for
ET from benzophenone ketyl or from sodium naphthalenide, for iron
catalyzed ET from a Grignard reagent to methyl iodide, and for
reduction of methyl iodide with tributyltin hydride or with
gaseous hydrogen iodide. Very small KIE's were found for electron
transfer to methyl iodide from magnesium in ether or from sodium
in ammonia. The reason may be that these reactions are transport
or diffusion controlled.
Original language | English |
---|---|
Journal | Journal of the American Chemical Society |
Volume | 121 |
Pages (from-to) | 515-518 |
ISSN | 0002-7863 |
Publication status | Published - 1999 |