Specific Chemical Conversion Based on the Cooperative Effect of Two Transition Metal Fragments in Close Proximity

（1） Irradiation of CpFe（CO） Irradiation of CpFe（CO）Irradiation of D22 SiMe D23 D（R = Et， Ph） afforded a silylene-bridged dinuclear complex Cp D22 D（CO）ID22 D（CO）ID22 D（-CO）{-Si（H）CHR I D22 D（R = Et， Ph）。On the other hand， irradiation of Cp*Fe（CO）イイD22イイD2SiMeイD23イイD2， which has bulky Cp* ligand， in the presence of PhイD22イイD2CHSiHイD23イD2 gave a mononuclear complex Cp*Fe（CO）イD22イイD2{Si（H）イD2 CHPhイD2} as a main product。通过与CpFe（CO）Y D22 Y D2 SiMe Y D23 Y D2 or CpW（CO）Y D23 Y D2 Me，我们成功地在不对称硅桥iron-iron and iron-tungsten复合体的选择性合成中Cp*（CO）Fe（μ-CO）{μ-Si（H）CHPh Y D22 Y D2}（CO）Y D2 n Y D2 MCp（M = Fe， n = 1 ; M = W， n = 2）。这种反应可能是一种不对称硅-桥接复合体的一般方法，这种方法是罕见的。（2）磷酸盐-桥接的铁-铁和铁-鲁瑟尼复合体的反应与各种烯烃进行了调查。作为一个结果，铁-铁复合体在其中一个或两个分子的烯烃组合成了一个碳基配体和一个磷酸配体形成一个桥接的配体，并结合了两个铁原子。产品类型的改变依赖于阿尔金、金属中心和支持的装备。在另一方面，铁-钌复合体提供的产品只在一个铝合金和一个碳基配体与铁和钌原子结合在一起。这些似乎是碳-碳和碳-磷键形成反应的新类型。他们的反应机制目前正处于调查之下。（3） Using disulfido-bridged diiron complexes as precursors， several new types of sulfur-bridged clusters containing metal cores of FeイイD22イイD2Ru， FeイD22イイD2Cr， FeイD22イエD2W， etc. were synthesized and the structures and fluxional behaviors of them were clarified。

(1) Irradiation of CpFe(CO)ィイD22ィエD2SiMeィイD23ィエD2 in the presence of trihydrosilane RィイD22ィエD2CHSiHィイD23ィエD2 (R = Et, Ph) afforded a silylene-bridged dinuclear complex CpィイD22ィエD2(CO)ィイD22ィエD2FeィイD22ィエD2(μ-CO){μ-Si(H)CHRィイD22ィエD2} (R = Et, Ph). On the other hand, irradiation of Cp*Fe(CO)ィイD22ィエD2SiMeィイD23ィエD2, which has bulky Cp* ligand, in the presence of PhィイD22ィエD2CHSiHィイD23ィエD2 gave a mononuclear complex Cp*Fe(CO)ィイD22ィエD2{Si(H)ィイD22ィエD2CHPhィイD22ィエD2} as a main product. By photoreaction of this mononuclear complex with CpFe(CO)ィイD22ィエD2SiMeィイD23ィエD2 or CpW(CO)ィイD23ィエD2Me, we succeeded in the selective synthesis of unsymmetrical silylene-bridge iron-iron and iron-tungsten complexes Cp*(CO)Fe(μ-CO){μ-Si(H)CHPhィイD22ィエD2}(CO)ィイD2nィエD2MCp (M = Fe, n = 1 ; M = W, n = 2). This reaction could become a general method of the synthesis of unsymmetrical silylene-bridged complexes which is rare.(2) Reactions of phosphido-bridged iron-iron and iron-ruthenium complexes with various alkynes were investigated. As a result, the iron-iron complexes yielded several types of complexes in which one or two molecules of alkynes were coupled with a carbonyl ligand and a phosphido ligand to form a bridging ligand that bridged two iron atoms. The product type changed depending on the alkyne, metal center, and supporting ligands. On the other hand, the iron-ruthenium complexes provided the products in which only an alkyne and a carbonyl ligand were coupled and bridged the iron and ruthenium atoms. These seem to be new types of carbon-carbon and carbon-phosphorus bond formation reactions. Their reaction mechanisms are currently under investigation.(3) Using disulfido-bridged diiron complexes as precursors, several new types of sulfur-bridged clusters containing metal cores of FeィイD22ィエD2Ru, FeィイD22ィエD2RuィイD22ィエD2, FeィイD22ィエD2Cr, FeィイD22ィエD2W, etc. were synthesized and the structures and fluxional behaviors of them were clarified.