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 o...

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Bibliographic Details
Published in:Physical chemistry chemical physics : PCCP 2006, Vol.8 (7), p.862-868
Main Authors: ADKINE, Prashant, CANTAT, Thibault, DESCHAMPS, Eliane, RICARD, Louis, MEZAILLES, Nicolas, LE FLOCH, Pascal, GEOLFFROY, Michel
Format: Article
Language:English
Subjects:
Atomic and molecular physics
Calculations and mathematical techniques in atomic and molecular physics (excluding electron correlation calculations)
Chemical Sciences
Chemistry
Density-functional theory
Electronic structure of atoms, molecules and their ions: theory
Exact sciences and technology
General and physical chemistry
or physical chemistry
Physics
Theoretical and
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Summary: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.
ISSN:1463-9076
1463-9084
DOI:10.1039/b513736p