Silyl-transition-metal complexes : Synthesis, Structure, Reactivity, and Application to Catalysis

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The reaction of bidentate and tridentate silyl ligand precursor hydrosilanes with group 10 transition-metal complexes was studied for the advancement of basic chemistry of silicon-transition-metal complexes and for the development of efficient catalysts for Si-Si bond forming reactions. The results showed that the chemistry of silicon-group 10 transition-metal complexes has a diversity beyond our expectation. Also we obtained important information for the development of catalysts for Si-Si bond forming reaction. The major results of this research are listed below.It was clarified that the reaction of the tridentate hydrosilane, (2-SiH_3C_6H_4)_2SiH_2,with group 10 transition-metal complexes provided diverse range of products depended on the metals and the steric hindrance of the ligands. We for the first time succeeded in the isolation and structure determination of a silylnickel complex that has a Ni^<IV>(H)(Si)_3 structure in the solid state while η^2-(Si-H)Ni structure in solution.・We succeeded in the isolation and structure determination of trinuclear and tetranuclear Pd complexes having Pd centers ligated by five Si atoms. This is the first example of Pd complex with a Pd center ligated by five formally anionic ligands.・The first example of Pt complex with cyclodisiloxane moiety was obtained by the reaction of the bidentate hydrosilane with a Pt(0) phosphine complex.・It was clarified that the reaction of the bidentate and the tridentate hydrosilanes with group 10 transition metal phosphine complexes was highly affected by the steric hindrance of phosphine ligands and of the hydrosilanes. If the steric hindrance is small, multinuclear complexes and high formal oxidation state complexes are easily formed. On the other hand, if the steric hindrance is severe, Si-Si bond forming reaction often takes place. This finding provides important information for the development of efficient catalysts for a Si-Si bond forming reaction.