G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, Tropinina, 49, Nizhny Novgorod, 603950, Russian Federation.
A.E.Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center, Russian Academy of Sciences, Arbuzov, 8, Kazan, 420088, Russian Federation.
Chemistry. 2019 Mar 12;25(15):3858-3866. doi: 10.1002/chem.201805427. Epub 2019 Feb 11.
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)] (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 ×(dioxane). In this case, complex (dpp-mian) SnCl (2) is formed, with the tin atom displaying an oxidation state of +4. Tin(II) chloride dihydrate, SnCl ×2(H 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). Metallic tin reduces dpp-mian to form the (bis-dpp-mian) Sn (4) species. Compounds 1-4 were characterized by X-ray diffraction.
2-单（2,6-二异丙基苯基亚氨基）-1-茚酮（dpp-mian）的电化学性质已被研究。dpp-mian 的单电子还原涉及亚胺酮片段，这是通过在四氢呋喃（THF）中电解 dpp-mian 溶液后获得的 EPR 光谱揭示的。用一当量的金属钾还原 dpp-mian 会导致类似的 EPR 光谱。钠配合物[(dpp-mian)Na(dme)]（1）在 dpp-mian 配体的亚胺酮片段的氮原子上产生具有超精细偶合的 EPR 信号。dpp-mian 也可以通过 SnCl×（dioxane）进行单电子还原。在这种情况下，形成配合物(dpp-mian)SnCl（2），其中锡原子显示+4 的氧化态。二水合氯化亚锡，SnCl×2（H2O），也还原 dpp-mian，但产物中与锡结合的两个配体在 dpp-mian 单阴离子的酮部分之间形成新的碳-碳键，形成配合物（双-dpp-mian）HSnCl（3）。金属锡将 dpp-mian 还原为（双-dpp-mian）Sn（4）物种。通过 X 射线衍射对化合物 1-4 进行了表征。
