Radicals Containing a Thiophene Ring

The electronic absorption spectrum of the cation-radical of thiophene itself has been observed following low-temperature y-radiolysis of the heterocycle in a Freon matrix.The radical has also been implicated in the oxidation of thiophene by dibenzoyl peroxide it is believed to be formed at the contact of certain transition metal layer-silicates with thiophene.The anodic oxidation of 2,5-dimethylthiophene has been studied by Japanese workers who found strong evidence for the formation of the cation-radical as the primary oxidation product.In the presence of strong nucleophiles such as cyanide ion, the cation-radical undergoes nucleophilic attack before further oxidation. In the presence of more basic species such as acetate ion, the cation-radical is deprotonated to give a thienylmethyl radical which undergoes further reaction. The results were compared with similar observations for the oxidation of 2,5-dimethylfuran. Czech workers have also studied the anodic oxidation of substituted thiophenes. This work has focused on the preparative value of anodic oxidations in acidified methanol. Cation-radical formation is implied for the primary step, but the value of the method lies in the fact that sulfur is ultimately eliminated from the substrate and functionalized y-dicarbonyl compounds result. 

Valentova, Collect. Czech. Chem. Commun. 35, 148 (1970). 

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Reviews have appeared in Italian and in English of radicals containing the thiophene ring system they deal with n- and a-radicals, respectively. 

Let us now direct our attention to the P=C bond in phosphaalkene ion-radicals. The literature contains data on two such anion-radicals in which a furan and a thiophene ring are bound to the carbon atom, and the 2,4,6-tri(tert-butyl)phenyl group is bound to the phosphorus atom. According to the ESR spectra of anion-radicals, an unpaired electron is delocalized on a n orbital built from the five-membered ring (furanyl or thienyl) and the P=C bond. The participation of the phosphaalkene moiety in this MO was estimated at about 60% and some moderate (but sufficient) transmission of the spin density occurs through the P=C bridge (Jouaiti et al. 1997). Scheme 1.6 depicts the structures under discussion. 

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