Chemistry of Transition Metal Supramolecules

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Several new diiron and iron-ruthenium complexes in which two metal units in different environments are bridged by a phosphido ligand have been synthesized. These complexes were found to react with various alkynes, dihydrosilanes, and hydrodisilanes under mild conditions to give the complexes in which these small molecules were incorporated as parts of newly formed ligands.The primary and secondary germanes were found to react with Cp'Fe (CO)_2SiMe_3 (Cp'=eta^5-C_5H_5, eta^5-C_5Me_5) upon UV irradiation to give mono-and bis (germylene) -bridged complexes. When the primary germane and the eta^5-C_5Me_5 complex were photolyzed, the unprecedented dinuclear complex with two Ge-H-Fe 3 center-2 electron bonds was also formed.New systematic synthesis of mixed-ligand and also mixed-metal transition metal-sulfur trinuclear and tetranuclear clusters has been achieved starting from sulfido-or disulfido-bridged diiron complexes.The facile 1,3-migration of substituents on a silylene-transition metal-silyl linkage (Si=M-Si) was confirmed for the first time by generating base-free silyl (silylene) complexes from base-stabilized ones on heating.The silyltetrakis (phosphine) iridium (I) complex was synthesized for the first time and it was found that this complex generates a 16-electron Ir (I) species by dissociation of a phosphine ligand at room temperature. This complex catalyzes the intramolecular rearrangement of substituents in hydrodisilanes to lead the isomerization. Starting from the same complex, the synthesis of the first silyl (silylene) complex of group 9 element has been achieved.