Synthesis of Heteroatom-Bridged Multinuclear Complexes and Application to Catalytic Transformations

点击翻译按钮获取中文摘要

Considerable attention has recently been paid to multimetallic complexes bridged by heteroatom ligands because of their potential applicability to various organic transformations. Recently, we disclosed a unique catalytic activity of thiolato- and selenolato-bridged diruthenium complexes [Cp^*RuCl(μ-YR)]_2 toward propargylic substitution reactions of propargylic alcohols with a variety of nucleophiles. In sharp contrast, tellurolato-bridged diruthenium complexes did not work as effective catalysts for these reactions, suggesting that the nature of bridging ligands plays an important role on the catalysis of these diruthenium complexes. These results prompted us to design and prepare other heteroatom-bridged diruthenium complexes. More recently, we succeeded in the preparation of the monophosphido-bridged diruthenium complex [Cp^*RuCl(μ-PMe_2)(μ-Cl)RuClCp^*] (1) and found a different catalytic activity of 1 from that of [Cp^*RuCl(μ-YR)]_2. In addition, 1 is expected to work as a useful precursor for diruthenium complexes bridged by different heteroatoms because 1 have a bridging chloride ligand which may easily be substituted with a variety of heteroatom ligands. In fact, we also succeeded in the preparation of a variety of hybrid phosphido- and thiolato-bridged complexes [Cp^*RuCl(μ-PMe_2)(μ-SR)RuClCp^*].