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Capture and Elimination of Reactive Intermediates on the Metalladichalcogenolene Rings

金属二硫属烯醇环上反应中间体的捕获和消除

基本信息

批准号：
09640673
负责人：
KAJITANI Masatsugu
金额：
$ 1.98万
依托单位：
Sophia University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1997
资助国家：
日本
起止时间：
1997 至 1998
项目状态：
已结题

项目摘要

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.

在[CpCo（S <$D22 <$D2C <$D22 <$D2XY）]型二硫代钴配合物中，由于不饱和度和芳香性，金属二硫烯环表现出多种反应活性。环进行加成反应，这归因于金属硫杂环戊烯环中的金属和硫原子之间的不饱和性（多键性）。乙炔二羧酸二甲酯、四环化合物、重氮化合物和叠氮化合物等可作为反应中间体的前体，在金属和硫之间形成烯烃、异烯烃、亚烷基和亚氨基桥连加合物，本文从反应中间体在金属硫杂环戊二烯环上的捕获和消除的角度，重点研究了亚烷基和亚氨基桥连加合物。它们进一步与刘易斯碱和质子酸反应，导致加合物中的三元环打开，得到相应的三组分加合物。有趣的是，键断裂依赖于攻击试剂和桥连基团的结构，我们详细研究了亚烷基和亚氨基桥连加合物及其三组分加合物的电化学行为，以及它们的光化学行为和它们与化学试剂的热活化。作为一个主题，磺酰亚胺桥加合物与三苯基膦的反应，导致亚氨基迁移到的双环。交叉实验表明，重排反应是一个分子间反应，表明氮烯物种的参与。