| Project/Area Number |
11640554
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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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 | Tohoku University |
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Principal Investigator |
UENO Keiji Graduate School of Science, Tohoku University, Research Associate, 大学院・理学研究科, 助手 (20203458)
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| Project Period (FY) |
1999 – 2000
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| Project Status |
Completed (Fiscal Year 2000)
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| Budget Amount *help |
¥3,400,000 (Direct Cost: ¥3,400,000)
Fiscal Year 2000: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 1999: ¥2,400,000 (Direct Cost: ¥2,400,000)
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| Keywords | Silylene Complexes / Germylene Complexes / Reactivity / Migration / Tungsten Complexes / Unsaturated Bonding / Isomerization / Isocarbonyl Complexes / ガリレン錯体 / 1,3-転移 / 動的挙動 |
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| Research Abstract |
1. Photolysis of Cp^*W(CO)_3Me (Cp^*=η-C_5Me_5) in the presence of excess HSiMe_2SiMe_3 afforded yellow crystals of a self-stabilized silyl (silylene) tungsten complex with a dimeric structure, [Cp^*W(CO)_2(=SiMe_2)(SiMe_3)]_2(1). In contrast, photolysis of Cp^*W(CO)_3Me in the presence of HSiMe_2SiMeMes_2 (Mes=2,4,6-Me_3C_6H_2) afforded a silyl (silylene) tungsten complex Cp^*W(CO)_2(=SiMes_2)(SiMe_3)(2). Complex 2 is the first "base-free" silyl (silylene) complex. X-ray crystal structure analysis of complex 1 and 2 revealed the significantly short W=Si bond compared to the W-Si bond. The ^<29> Si NMR signal of the silylene ligand for 2 appeared at remarkably low field (δ380.9 ppm) with a tungsten satellite having a large coupling constant (^1J_<SiW>=154.9 Hz). These results clearly demonstrate the double bond character of tungsten-silylene bonding.
2. Photolysis of Cp^*W(CO)_3GeMe_2GeMe_3 resulted in the formation of a "base-free" germyl (germylene) tungsten complex Cp^*W(CO)_2(=GeMe_2)(GeMe_3)(3) quantitatively. Complex 3 is the first germylene complex having only small methyl groups on the germanium atoms. Reaction of complex 3 with Fe_2(CO)_9 resulted in the formation of a germylene-bridged dimetal complex Cp^*(OC)_3W(μ-GeMe_2)Fe(CO)_3GeMe_3 quantitatively.
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