Remote Control of Electron Transfer Reaction by Microwave
Irradiation: Kinetic Demonstration of Reduction of Bipyridine Derivatives
on Surface of Nickel Particle
posted on 2019-05-03, 00:00authored byFuminao Kishimoto, Masayuki Matsuhisa, Takashi Imai, Dai Mochizuki, Shuntaro Tsubaki, Masato M. Maitani, Eiichi Suzuki, Yuji Wada
Microwave
irradiation has great potential to control chemical reactions
remotely, particularly reactions that involve electron transfer. In
this study, we found that the reduction reaction of bipyridine derivatives
on metal nickel particles was accelerated or decelerated by 2.45 GHz
microwaves without an alteration of the reaction temperature. The
order of the extent of the microwave acceleration of the electron
transfer reaction coincided with the negativity of the redox potential
of the bipyridine derivatives, i.e., the electron transfer with smaller
ΔG was significantly enhanced by microwave
irradiation. By applying Marcus’ electron transfer theory,
we propose two mechanisms of the microwave effect on electron transfer
reactions, i.e., vibration of the electrons in Ni particles to make
the electron transfer easier and rotation of the water molecules to
prevent the reorganization of the hydrated systems after the electron
transfer reaction.