Characterization of transient radicals in the reduction product of the –PCCP– system: EPR and theoretical studies

Helena Sidorenkova; Mostafa Chentit; Sylvie Choua; Michel Geoffroy; Yves Ellinger

doi:10.1039/B205848K

Characterization of transient radicals in the reduction product of the –PCCP– system: EPR and theoretical studies

Helena Sidorenkova,^a Mostafa Chentit,^a Sylvie Choua,^a Michel Geoffroy*^a and Yves Ellinger*^b

Author affiliations

* Corresponding authors

^a Department of Physical Chemistry, University of Geneva, 30 Quai Ernest Ansermet, Geneva, Switzerland

^b Laboratoire d'Etude Théorique des Milieux Extrèmes, Université de Nice-Sophia Antipolis et Observatoire de la Côte d'Azur, Nice, France

Abstract

The EPR spectrum obtained at room temperature after electrochemical or chemical reduction of a solution of Ar–P [double bond, length half m-dash] CCP–Ar in THF exhibits hyperfine interaction (165 MHz) with two equivalent ³¹P nuclei. Additional couplings with two equivalent ¹³C are observed with Ar–P¹³C¹³CP–Ar. The ³¹P anisotropic coupling constants could be obtained from spectra recorded at low temperature. They indicate that the unpaired electron is mainly localized (78%) on the two phosphorus atoms. Quantum chemical calculations (DFT and ab initio SCI) were performed on the various isomers of the two radical anions: [H–P [double bond, length half m-dash] CCP–H]˙⁻ and [H–PCH–CHP–H]˙⁻. Although the optimized geometries of these two species are clearly different, neither of them leads to ¹³C/³¹P hyperfine tensors in conflict with the experimental results. The absence of any ¹H splitting on the EPR spectrum together with the quasi-reversibility of the reduction wave make the identification of [Ar–P [double bond, length half m-dash] CCP–Ar]˙⁻ more probable.

Article information

https://doi.org/10.1039/B205848K

Article type

Paper

Submitted

17 Jun 2002

Accepted

20 Aug 2002

First published

18 Sep 2002

Download Citation

Phys. Chem. Chem. Phys., 2002,4, 4931-4936

Permissions

Request permissions

Characterization of transient radicals in the reduction product of the –PCCP– system: EPR and theoretical studies

H. Sidorenkova, M. Chentit, S. Choua, M. Geoffroy and Y. Ellinger, Phys. Chem. Chem. Phys., 2002, 4, 4931 DOI: 10.1039/B205848K

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Physical Chemistry Chemical Physics

Characterization of transient radicals in the reduction product of the –PCCP– system: EPR and theoretical studies

Abstract

Article information

Download Citation

Permissions

Characterization of transient radicals in the reduction product of the –PCCP– system: EPR and theoretical studies

Social activity

Search articles by author

Spotlight

Advertisements