Issue 7, 2006
From the journal:

Physical Chemistry Chemical Physics

EPR and DFT studies of the one-electron reduction product of phospholium cations

Prashant Adkine,a   Thibault Cantat,b   Eliane Deschamps,b   Louis Ricard,b   Nicolas Mézailles,b   Pascal Le Floch*b  and  Michel Geoffroy*a  

* Corresponding authors

a Department of Physical Chemistry, University of Geneva, 30 Quai Ernest Ansermet, Geneva, Switzerland
E-mail: michel.geoffroy@chiphy.unige.ch

b Laboratoire “Hétéroéléments et Coordination”, UMR 7653, Ecole Polytechnique, Palaiseau Cédex, France
E-mail: lefloch@poly.polytechnique.fr

Abstract

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.

Graphical abstract: EPR and DFT studies of the one-electron reduction product of phospholium cations

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Article information

DOI
https://doi.org/10.1039/B513736P
Article type
Paper
Submitted
27 Sep 2005
Accepted
07 Dec 2005
First published
19 Dec 2005

Phys. Chem. Chem. Phys., 2006,8, 862-868

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EPR and DFT studies of the one-electron reduction product of phospholium cations

P. Adkine, T. Cantat, E. Deschamps, L. Ricard, N. Mézailles, P. Le Floch and M. Geoffroy, Phys. Chem. Chem. Phys., 2006, 8, 862 DOI: 10.1039/B513736P

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