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Scientific article
English

9-substituted triptycene as a probe for the study of internal rotation around a C-PH bond in the solid state : a single crystal EPR study at variable temperature

Published inJournal of physical chemistry. C, vol. 100, no. 26, p. 10861-10868
Publication date1996
Abstract

To measure the rotation barrier around an R3C−•PH bond in the solid state, 9-phosphinotriptycene50 2 has been synthesized and its crystal structure has been determined. It is shown, by EPR, that the radiogenic radical 3, which results from a homolytic scission of a P−H bond, can indeed be trapped in the crystal matrix. Its g-tensor together with its 31P and 1H hyperfine coupling have been measured at 300 and 77 K. These tensors show that free rotation around the C−P bond occurs at room temperature but is blocked at liquid nitrogen temperature. The temperature dependence of the EPR spectra has been analyzed using the density matrix formalism and has led to a rotation barrier of about 2.5 kcal·mol-1. This result and the various hyperfine couplings have been compared with the values predicted by ab initio methods for two isolated model radicals: the tert-butylphosphinyl radical 4 and the barrelenophosphinyl radical 5.

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Citation (ISO format)
RAMAKRISHNAN, Geetha et al. 9-substituted triptycene as a probe for the study of internal rotation around a C-PH bond in the solid state : a single crystal EPR study at variable temperature. In: Journal of physical chemistry. C, 1996, vol. 100, n° 26, p. 10861–10868. doi: 10.1021/jp960836h
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ISSN of the journal1932-7447
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