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Title

Using the Diphosphanyl Radical as a Potential Spin Label: Effect of Motion on the EPR Spectrum of an R1(R2)P--PR1 Radical
Authors
Cataldo, Laurent
Dutan, Cosmina
Misra, Sushil K.
Loss, Sandra
Grützmacher, Hansjörg
Geoffroy, Michel
Published in Chemistry - A European Journal. 2005, vol. 11, no. 11, p. 3463-3468
Abstract The EPR spectrum of the novel radical Mes*(CH3)PPMes* (Mes*=2,4,6-(tBu)3C6H2) was measured in the temperature range 100-300 K, and was found to be drastically temperature dependent as a result of the large anisotropy of the 31P hyperfine tensors. Below 180 K, a spectrum of the liquid solution is accurately simulated by calculating the spectral modifications due to slow tumbling of the radical. To achieve this simulation, an algorithm was developed by extending the well-known nitroxide slow-motion simulation technique for the coupling of one electron spin to two nuclear spins. An additional dynamic process responsible for the observed line broadening was found to occur between 180 K and room temperature; this broadening is consistent with an exchange between two conformations. The differences between the isotropic 31P couplings associated with the two conformers are shown to be probably due to an internal rotation about the PP bond.
Keywords EPR spectroscopy — Internal rotation — Phosphorus — Radicals — Spin labeling
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Other version: http://www3.interscience.wiley.com/cgi-bin/fulltext/110444582/PDFSTART
Structures
Faculté des sciences / Section de chimie et biochimie / Département de chimie physique
Research group Groupe Geoffroy
Citation
(ISO format) 		CATALDO, Laurent et al. Using the Diphosphanyl Radical as a Potential Spin Label: Effect of Motion on the EPR Spectrum of an R1(R2)P--PR1 Radical. In: Chemistry - A European Journal, 2005, vol. 11, n° 11, p. 3463-3468. https://archive-ouverte.unige.ch/unige:3277

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Deposited on : 2009-09-21

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