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

本研究描述了利用空间排列的含多个碳原子的有机化合物制备具有2中心-2电子[2c-2e]体系的指示物和具有3中心-4电子[3c-4e]键的高配位指示物。在硫原子上被烷基和苯基取代的[2c-2e]的指示具有很强的反应性，它们的形成要么未被检测到，要么只能通过低温^ 1h和^<13>C-nmr谱检测到。这些指示物一旦形成，易脱烷基反应生成n -烷基乙酰胺，这些n -烷基乙酰胺被CH_3CN捕获，与硫磺酸盐一起用作溶剂，产率高。这种脱烷基反应的机制可以合理地解释为通过s_nl型取代机制进行。另一方面，萘[1,8-de] -1,3-二硫胺的单氧化物、单n -甲基亚亚胺和单s -酰基化合物的光解定量地提供了相应的酮、n -亚胺和烯烃。通过激活这些化合物的S-S相互作用，可以进行更多的光解作用。对于高配位的[3c-4e]化合物，1-苯基2,6-二甲基硫代甲基苯基碲化物在氧化作用下转化为碲化物。同样，1,11-甲基硒-[或硫]二硫辛酸（或二硫辛酸）在用NOBF_4等电子氧化剂处理二硫辛酸（或二硫辛酸）时，可得到相应的硒脲（或硫烷）化合物。这些[3c-4e]高价指示物可以通过还原指示物很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。这些指示足够稳定，可以被分离出来，并通过x射线晶体学分析确定了它们的结构。这些化合物的从头计算揭示了高价分子中原子间的电荷分布，并讨论了它们的反应性。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