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

(1) Irradiation of CpFe(CO) - D22 - D2SiMe - D23 - D2 in the presence of trihydrosilaneD22 D2CHSiH D23 dd2 (R = Et，Ph) afforded a silylene-bridged dinuclear complexD22 - D2(CO) D22 - D2Fe - D22 - D2(μ-CO){μ-Si(H)CHR - D22 - D2} (R = Et, Ph). On the other hand，irradiation of Cp*Fe(CO) - D22 - D2SiMe - D23 - D2, which has bulky Cp* ligand，in the presence of phy D22 D2CHSiH D23 D2 gave a mononuclear complexCp*Fe(CO) - D22 - D2{Si(H) - D22 - D2CHPh - D22 - D2} as a main product. By photoreaction of thismononuclear complex with CpFe(CO) D22 D2SiMe D23 D23 D2 or CpW(CO) D23 D2Me，we succeeded in the selective synthesis of unsymmetrical silylene-bridge iron-iron and iron-tungstencomplexes Cp*(CO)Fe(μ-CO){μ-Si(H) chphi D22 - D2}(CO) i D2n - D2MCp (M = Fe, n = 1；M = W，n = 2). This reaction could become a general method of the synthesis of unsymmetricalsilylene-bridged complexes which is rare.(2) Reactions of phosphido-bridged ironiron andironruthenium complexes with various alkynes investigated. As a result，the ironiron complexes yielded several types of complexes in which one or two molecules of alkynescoupled with a carbonyl ligand a phosphido ligand to form a bridging ligand that bridged两个钢铁原子。The product type changed depending on The alkyne, metal centerand supporting ligands. On the other hand，ironruthenium complexes provided the products in which only an alkyne and a carbonyl ligandcoupled and bridged the iron and ruthenium atoms.这些seem to be be new types of carbon-carboncarbon-phosphorus bond formation reactions.他们的反应机制是currently underinvestigation.(3) Using disulfido-bridged diiron complexes as precursors，several new types of sulfur-bridged clusters containing metal cores of Fe D2RuFe - D22 D2Ru D22 - D2, Fe - D22 - D2Cr, Fe - D22 - D2W，他们被联合起来，结构和影响环境等。

(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.