One‐Electron Reduction of 2‐Mono(2,6‐diisopropylphenylimino)acenaphthene‐1‐one (dpp‐mian)

The electrochemical characteristics of 2‐mono(2,6‐diisopropylphenylimino)acenaphthene‐1‐one (dpp‐mian) have been investigated. One‐electron reduction of dpp‐mian involves the iminoketone fragment, which is revealed by the EPR spectrum obtained after the electrolysis of the dpp‐mian solution in tetrahydrofuran (THF). The reduction of dpp‐mian with one equivalent of metallic potassium leads to a similar EPR spectrum. The sodium complex [(dpp‐mian)Na(dme)] 2 ( 1 ) produces an EPR signal with hyperfine coupling on the nitrogen atom of the iminoketone fragment of the dpp‐mian ligand. Dpp‐mian can also be reduced in a one‐electron process by SnCl 2 ×(dioxane). In this case, complex (dpp‐mian) 2 SnCl 2 ( 2 ) is formed, with the tin atom displaying an oxidation state of +4. Tin(II) chloride dihydrate, SnCl 2 ×2(H 2 O), also reduces dpp‐mian, but the two ligands bound to tin in the product form a new carbon–carbon bond between the ketone moieties of the dpp‐mian monoanions to form complex (bis‐dpp‐mian)HSnCl 3 ( 3 ). Metallic tin reduces dpp‐mian to form the (bis‐dpp‐mian) 2 Sn ( 4 ) species. Compounds 1 – 4 were characterized by X‐ray diffraction.