ジシラメタラサイクル骨格の構築を基盤とする錯体開発

抄録

In this review, synthesis and applications of a series of novel transition metal complexes bearing the disilametallacycle skeleton have been reported. The first topic is the synthesis of an iron(II)-dicarbonyl complex 4 having 1,2-bis(dimethylsilyl)benzene as the chelating organosilyl ligand. This complex demonstrated high catalytic activity toward the reduction of various carbonyl compounds such as carboxamides, aldehydes, ketones and esters by using hydrosilane as the reducing reagent. Complex 4 also realized the catalytic hydrogenation and hydrosilylation of alkenes, and C-3 selective C-H bond silylation of indole derivatives. Second, a template synthesis of “folding” metal nanosheet molecule consisting of eleven palladium atoms by treatment of a ladder polysilane with Pd(CN^tBu)₂ is described. Single crystal X-ray diffraction analysis reveals that this cluster is composed of two monolayer Pd₇ sheets sharing three palladium atoms at the junction. Ligand exchange of this cluster from CN^tBu to CN(2,4,6- Me₃-C₆H₂) is accompanied by structural rearrangement, leading to formation of another “folding” Pd₁₁ nanosheet, and the atomic arrangement in Pd₁₁ sheet as well as the dihedral angle of two Pd₇ sheets is dependent on the substituent of the isocyanide ligand.