Studies on the Active Molecules Prepared by Accumulation and Amplification of the Transannular Interaction between Chalcogen Atoms

在这项研究中，描述了用空间排列的含多个硫族原子的有机化合物制备具有2-中心-2-电子[2c-2e]体系和具有3-中心-4-电子[3c-4e]键的高配位化合物。[2c-2e]在硫族原子上被烷基和苄基取代的反应是非常活跃的，它们的形成要么没有被检测到，要么只有通过低温~1H和~(13)&lt；C-核磁共振才能检测到。这些化合物一旦形成，就可以容易地进行脱烷基反应，得到N-烷基乙酰胺，这些N-烷基乙酰胺被CH_3CN作为溶剂与硫磺盐一起高产率地捕获。合理地解释了该脱烷基反应的机理为S_NL型取代机理。另一方面，1，8-De-1，3-二硫杂环己烷的单氧化物、单N-甲苯磺亚胺和单S叶立德的光解定量提供了相应的酮、N-亚胺和烯烃。光解Re…更多的作用可能通过激活这些化合物的S-S相互作用而进行。对于高配位的[3c-4e]配位物种，1-苯基-2，6-二甲基硫甲基苯基碲化物在氧化过程中转化为碲烷。类似地，1，11-亚甲基硒-[或-硫代]二硒素(或二硫代谢素)在用一种电子氧化剂如NOBF_4处理二硒素(或二硫代谢素)时得到相应的硒(或硫烷)化合物。这些[3c-4e]高价离子可通过还原反应容易地转化为起始的三硒化物(或硫化物)。在这些三硒化物(或硫化物)的氧化还原反应中，这些化合物在氧化还原过程中表现出分子滞后。这些化合物非常稳定，可以进行分离，其结构经X-射线晶体分析确定。这些化合物的从头算揭示了超价分子中原子间的电荷分布，并与它们的反应活性进行了讨论。较少

In this studies, it was described the preparation of the dications having 2-center-2-electron [2c-2e] system and highcoordinated dications having 3-center-4-electron [3c-4e] bonds using organic compounds bearing multiple-chalcogen atoms arranged in space. The dications of [2c-2e] substituted by alkyl and benzyl groups at the chalcogen atoms were found to be quite reactive, and their formation was either undetected or detected only by low temperature ^1H-and ^<13>C-nmr spectroscopy. These dications once formed undergo facile dealkylation to afford N-alkyl acetamides which are trapped by CH_3CN used as a solvent together with thia-sulfonium salts in high yields. The mechanism for this dealkylation is rationally explained to proceed via an S_Nl-type substitution mechanism. On the other hand, the photolysis of the monooxides, mono-N-tosylsulfilimines and mono-S-ylides of naphtho [1,8-de] -1,3-dithiin provided the corresponding ketones, N-imines and olefins quantitatively. The photolysis re … More actions may proceed via the activation of the S-S interaction of these compounds. As to the highcoordinated [3c-4e] dication species, 1-phenyl 2,6-dimethylthiomethylphenyl tellurides were converted to the telluranes on oxidation. Similarly, 1,11-methanoseleno- [or-thio] diselenocin (or dithiocin) afforded the corresponding selenurane (or sulfurane) compounds on treatment of the diselenocin (or dithiocin) with one electron oxidant such as NOBF_4. These [3c-4e] hypervalent dications can be converted readily to the starting tris-selenides (or sulfides) by reducing the dications. In these oxidation-reduction reactions of the trisselenides (or sulfides), these compounds show molecular hysteresis during oxidation-reduction. The dications were stable enough to be isolated and their structures were determined by X-ray crystallographic analysis. The ab initio MO-calculation of these compounds reveal the charge-distribution among the atoms in the hypervalent molecules which was discussed with their reactivities. Less