Journal of the American Chemical Society p. 1027 - 1032 (1986)
Update date:2022-08-03
Topics:
Nelsen, Stephen F.
Kapp, Daniel L.
Gerson, Fabian
Lopez, Javier
The radical cation formed upon electrochemical oxidation either of adamantylideneadamantane 1 in an O2-saturated solution or of the corresponding dioxetane 2 is shown by ESR spectroscopy to be 2+.This radical cation is relatively long-lived in CH2Cl2:CF3CO2H:(CF3CO)2O solvent mixtures at low temperatures.The resolved hyperfine splittings are 0.325 mT (4H) and 0.075 mT (6H).Using deuterated derivatives, the larger splitting has been assigned to two pairs of γeq-protons and the smaller one to the two remaining pairs of γeq-protons and one pair of β-protons, with each β-proton situated in a different adamantylidine moiety of 2+ (the notation β and γeq refers to the stucture of 1).These data are consistent with a C2 conformation of 2+ which is twisted at the dioxetane ring and does not enantiomerize on the hyperfine time scale at -110 deg C.Dioxetane radical cations 11+ and 13+ generated from isopropylideneadamantane 10 and 3-pentylideneadamantane 12, respectively, have also been studied under similar conditions by ESR spectroscopy.Their hyperfine data give no evidence of twisting at the dioxetane rings and provide a further example for the sensitivity of the long-range splittings to orientation of bonds relative to the spin-bearing orbital.Cyclic voltammograms indicate that the Eo' value for 2 is 0.66 V anodic of 1 at -78 deg C, so that electron transfer from 1 to 2+ is exothermic by 15 kcal/mol.
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