| Project/Area Number |
62470087
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| Research Category |
Grant-in-Aid for General Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Research Field |
Synthetic chemistry
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| Research Institution | HIROSHIMA UNIVERSITY |
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Principal Investigator |
MITSUO Ishikawa Department of Applied Chemistry, Faculty of Engineering, Hiroshima University, Professor, 工学部, 教授 (20025985)
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| Project Period (FY) |
1987 – 1988
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| Project Status |
Completed (Fiscal Year 1988)
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| Budget Amount *help |
¥6,000,000 (Direct Cost: ¥6,000,000)
Fiscal Year 1988: ¥1,600,000 (Direct Cost: ¥1,600,000)
Fiscal Year 1987: ¥4,400,000 (Direct Cost: ¥4,400,000)
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| Keywords | Silylene / Nickelasilacyclobutene / C-H bond activation / ニッケラシラシクロブテン / CーH結合活性化 / 遷移金属錯体 / ニッケル / 鉄 / ルテニウム / シラプロパジエンーニッケル錯体 / ケイ素ー炭素二重結合化学種 |
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| Research Abstract |
We have demonstrated that the reaction of l-mesityl-3-phenyl-1,2-bis(tri-methylsilyl)-1-silacyclopropene with 1 equiv of tetrakis(triethylphosphine)-nickel(0) affords nickelasilacyclobutene (1) in almost quantitative yield. Compound 1 involves a nickel atom and a silicon atom in the four-membered cyclic system and seems to be useful for synthetic chemistry, as well as structural chemistry.
Thermolysis of 1 led to the formation of a silapropadiene-nickel complex which underwent further isomerization to give two isomers of a benzodisilacyclo-hexene, 3 and 4, via intramolecular C-H bond activation of a mesityl group. The photolysis of 1 also gave 3 and 4.
We have investigated the reaction of 2-phenylethynyl-2-(o-tolyl)hexamethyl-trisilane (2) with a nickel catalyst. Heating 2 with a catalytic amount of tetrakis(triethylphosphine)nickel(0) at 220゜C gave benzodisilacyclohexenes analogous to 3 and 4. Whereas at 260゜C, 2 produced a silylene-nickel complex which could be trapped by methyldiphenylsilane. Similar treatment of 2 with a catalytic amount of an iron-complex in the presence of methyldiphenylsilane as a trapping agent afforded a product arising from insertion of the silylene-iron complex into an Si-H bond of the hydrosilane.
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