EPR and DFT studies of the one-electron reduction product of phospholium cations.
Cyclic voltammetry and EPR spectroscopy show that cationic phospholium groups are good electron acceptors whose reduction leads to a neutral radical where the unpaired electron is mainly delocalized on the carbon atoms of the five-membered ring. DFT calculations together with the crystal structure of phospholiums indicate that the electron addition causes a drastic diminution of the exocyclic CPC angle. The SOMO of reduced phospholium is compared to the SOMO of the phosphole radical anion.
Adkine
Prashant
P
Department of Physical Chemistry, University of Geneva, 30 Quai Ernest Ansermet, 1211 Geneva, Switzerland.
Cantat
Thibault
T
Deschamps
Eliane
E
Ricard
Louis
L
Mézailles
Nicolas
N
Le Floch
Pascal
P
Geoffroy
Michel
M