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.
Department of Physical Chemistry, University of Geneva, 30 Quai Ernest Ansermet, 1211 Geneva, Switzerland.
Prashant
P
Adkine
Thibault
T
Cantat
Eliane
E
Deschamps
Louis
L
Ricard
Nicolas
N
Mézailles
Pascal
P
Le Floch
Michel
M
Geoffroy