| Project/Area Number |
16350028
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Inorganic chemistry
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| Research Institution | Tokyo Institute of Technology |
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Principal Investigator |
OSAKADA Kohtaro Tokyo Institute of Technology, Checmial Resources Laboratory, Professor, 資源化学研究所, 教授 (00152455)
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| Project Period (FY) |
2004 – 2005
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| Project Status |
Completed (Fiscal Year 2005)
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| Budget Amount *help |
¥15,500,000 (Direct Cost: ¥15,500,000)
Fiscal Year 2005: ¥6,500,000 (Direct Cost: ¥6,500,000)
Fiscal Year 2004: ¥9,000,000 (Direct Cost: ¥9,000,000)
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| Keywords | Platinum / Si-ligand / Ge-ligand / Cluster / Bridging Ligand / Silylene Complex / Germylene Complex / ケイ素 / ゲルマニウム / シリレン / ゲルミレン / パラジウム / 多核錯体 / 銅 |
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| Research Abstract |
This research project aims to synthesize novel tetranuclear platinum and palladium complexes having bridging diarylsilylene ligands and to determine the unique planar structures. Dinuclear Pd and Pt complexes with bridging silylene ligands are obtained with the procedure Which were reported by our group as well as the research group in the States. For example, Pt(PCy_3)_2 functions as a convenient precursor of the dinuclear Pt(I) complexes with two bridging silyl ligands. Heterodinuclear Pd-Pt complex with bridging diphenylsilyl ligand is also obtained from a mixture of Pd(O) and Pt(O) complexes. Reaction of a chelating diphosphine ligand with the dinuclear complexes afforded the Pt_4 complexes and Pt_3Pd complexes. The molecular structures of these complexes have been revealed by X-ray crystallography and by detailed NMR measurement of the solutions. The obtained complexes have four Pt(O) or Pd(O) centers bonded with bridging silylene ligands and metal-metal bonding. Bond lengths and angles show high symmetrical planar structures of the complexes. The DFT calculation for the complexes revealed that the tetranuclear core consists of the zero valent metal centers and neutral silylene ligands. Analogous Pd complexes with bridging diarylgermylene ligands have also been prepared and characterized.
The above reaction, forming the tetranuclear complexes, has been followed by the NMR spectroscopy. The reaction is induced by exchange of the monodentate phosphine ligand with the chelating diphosphine ligand. The subsequent condensation of the dinuclear complexes accompanies conversion of the silyl ligand to silylene ligand or germyl ligand to digermene ligand, which leads to formation of the tetranuclear complexes.
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