AbstractThe radical anions of [2.2]paracyclophane‐1,9‐diene (2) and its 1,10,12,13,15,16‐hexadeuterio derivative 2‐D6, as well as those of 4,5,7,8‐tetramethyl[2.2]paracyclophane‐1,9‐diene (3) and its 12,13,15,16‐tetradeuterio derivative 3‐D4, have been studied by ESR spectroscopy. The coupling constants for 2−· at 178 K are 0.422 mT for four equivalent olefinic protons and 0.046 and 0.020 mT, each for a set of four equivalent aromatic protons. This hyperfine pattern is consistent with either benzene ring bearing two pairs of equivalent protons and it points to a lowering of the anticipated D2h symmetry. The ESR spectra of 2−· are strongly temperature dependent, due to modulation of the two coupling constants of 0.046 and 0.020 mT; these have opposite signs and average to 0.013 mT at 273 K. The experimental findings are interpreted in terms of a transition state of D2h symmetry, 33 kJ/mol above two interconverting equivalent conformations of lower symmetry. Several pieces of evidence suggest that this symmetry is D2, i.e., the benzene rings in 2−· are twisted in opposite directions about the vertical axis. Temperature dependence of the ESR spectra, resulting from modulation of the hyperfine interactions with the aromatic protons, is also observed for 2‐D6−· and 3−·. In the case of 3−·, the olefinic protons are, as expected, only equivalent in pairs, the pertinent coupling constants being 0.560 and 0.325 mT. Upon standing at low temperatures, 2−· and 3−· gradually convert into the radical anions of [2.2]paracyclophane (1) and its 4,5,7,8‐tetramethyl derivative, respectively. At higher temperatures, cleavage of one bridging chain in 2−· also occurs, with the formation of the radical anion of (E)‐4,4′‐dimethylstilbene (7). Both reactions of 2−· must involve the transient radical anion of [2.2]paracyclophane‐1‐ene (4) as proved by the observation of the spectra of 1−· and 7−· with 4 as the starting material.