Alkali N.M.R. experiments on the radical ion pairs of biphenyl and fluorenone

Abstract

Line widths in the ⁶Li, ⁷Li, ²³Na, ³⁹K, ⁸⁵Rb, ⁸⁷Rb and ¹³³Cs N.M.R. spectra of solutions of the alkali salts of biphenyl and fluorenone are reported as a function of solvent and temperature. From a numerical analysis of the room temperature data the contribution of the various relaxation mechanisms to the line widths are established. It is shown that the results are consistent with the observed solvent and temperature dependence of the line widths. Values of the electron spin correlation time are obtained and a value of 1·6 ± 0·4 Å is found for the ‘Van der Waals radius’ of the biphenyl anion. Line width expressions for the static and the dynamic ion pair model are presented. It is demonstrated that the static ion pair model applies to solutions of caesium biphenylide. Semi-empirical rules are presented concerning the importance of various relaxation mechanisms for the different alkali nuclei in the type of solution studied here.