Journal of Physical Chemistry, Vol.100, No.26, 10861-10868, 1996
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
To measure the rotation barrier around an R(3)C-(PH)-P-. bond in the solid state; 9-phosphinotriptycene(50) 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 P-31 and H-1 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.