Capture and Elimination of Reactive Intermediates on the Metalladichalcogenolene Rings

metalladithiolene ring in [CpCo（S-D22-D2C-D2XY）]-type dithiolatocobalt complexes show a variety of reactivities due to unsaturation and due to aromaticity。The Rings Unergo the addition reactions which are ascribed to the unsaturation （multi bond plicity） Between the metal and sulfur atoms in the metalladithiolene rings。二甲基乙酰化羧基、四甲基化化合物、二氮化合物和叠氮化合物，可以使用作为反应性中间体之间金属和硫基的预固化剂，以形成烯烃-、北硼-、烯烃-和中间桥接的添加剂。在这一工作中，我们的注意力主要集中在烯烃和中间桥接的添加剂从捕获和消除金属氢化物戒指上反应性中间体的临界点。它们进一步与刘易斯基和原酸发生反应，结果是在打开的三个成员环中添加到相应的三个组分添加物中。有趣的是，这种粘合剂的清除取决于攻击性试剂和桥接组的结构，我们对烷基-和中间-混合的电荷及其三个组成部分的电荷进行了详细的研究，包括它们的光化学行为及其与化学-反应的热激活。作为一个主题，与三苯酰磷酸盐相结合的添加剂的反应在中等群体迁移到环戊二烯环的过程中。从一个交叉的实验中，这种重新排列被包括在一个间分子反应中，建议参与硝酸盐物种。

The metalladithiolene ring in [CpCo(SィイD22ィエD2CィイD22ィエD2XY)]-type dithiolatocobalt complexes show a variety of reactivities due to unsaturation and due to aromaticity. The rings undergo the addition reactions which are ascribed to the unsaturation (multi bond plicity) between the metal and sulfur atoms in the metalladithiolene rings. Dimethyl acetylenedicarboxylate, quadricyclanc, diazo compounds, and azide compounds which were able to use as precursors of reactive intermediates bridge between metal and sulfur to form alkene-, norbornene-, alkylidene-, and imido-bridged adducts.In this work, our attention was focused especially on alkylidene and imido-bridged adducts from the standpoint of capture and elimination of reactive intermediates on the metalladichalcogenolene rings. They further react with Lewis bases and protic acids, resulting in the opening of the three-membered rings in adducts to afford the corresponding three-component adducts. Interestingly, the bond cleaved is dependent on the attacking reagents and on the structures of the bridging groups.We investigated in detail the electrochemical behavior of alkylidene- and imido-bridged adducts and their three-component adducts, together with their photochemical behavior and their thermal activation with chemical reagents. As a topic, the reaction of the sulfonylimido-bridged addut with triphenylphosphine resulted in the migration of imido group to the cyclopentadienyl ring. From a cross over experiment, the rearrangement has been concluded to be an intermolecular reaction, suggesting the participation of nitrene species.