| Project/Area Number |
14078208
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| Research Category |
Grant-in-Aid for Scientific Research on Priority Areas
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| Allocation Type | Single-year Grants |
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| Review Section |
Science and Engineering
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| Research Institution | Tokyo University of Agriculture and Technology |
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Principal Investigator |
KOMIYA Sanshiro Tokyo University of Agriculture and Technology, Institute of Symbiotic Science and Technology, Professor, 共生科学技術研究院, 教授 (00111667)
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| Co-Investigator(Kenkyū-buntansha) |
HIRANO Masafumi Tokyo University ofAgriculture and Technology, Institute of Symbiotic Science and Technology, Associate Professor, 共生科学技術研究院, 助教授 (70251585)
KOMINE Nobuyuki Tokyo University ofAgriculture and Technology, Institute of Symbiotic Science and Technology, Associate Professor, 共生科学技術研究院, 助手 (90302918)
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| Project Period (FY) |
2002 – 2005
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| Project Status |
Completed (Fiscal Year 2006)
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| Budget Amount *help |
¥29,400,000 (Direct Cost: ¥29,400,000)
Fiscal Year 2005: ¥7,200,000 (Direct Cost: ¥7,200,000)
Fiscal Year 2004: ¥7,200,000 (Direct Cost: ¥7,200,000)
Fiscal Year 2003: ¥7,500,000 (Direct Cost: ¥7,500,000)
Fiscal Year 2002: ¥7,500,000 (Direct Cost: ¥7,500,000)
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| Keywords | hydrido palladirm-molybdenum complex / hvdridomolybdenum complex / insertion reaction / zero-valent palladium complex / 有機パラジウム-コバルト二核錯体 / アジリジン / 共重合反応 / 異種金属間の共同効果 / メチル白金-コバルト二核錯体 / チエタン / カルボニル化 / ヘテロ遷移金属錯体 / 異種金属間協同効果 / 酸化的付加 / 白金 / コバルト |
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| Research Abstract |
Reaction of (dppe)HPd-MoCp(CO)_3 with ethyl Reaction of (dppe)HPd-MoCp(CO)_3 with ethyl acrylate caused immediate reductive elimination of the hydridomolybdenum complex MoHCp(CO)_3. In this reaction, further Markovnikov addition of the metal hydride to ethyl acrylate slowly took place to give an insertion product Mo[CH(CO_2Et)Me]Cp(CO)_3. In the presence of Pc1(η^2-CH_2=CHCO_2Et)(dppe) or Pd(PPh_3)_4, smooth catalytic insertion of olefin into Mo-H bond has been achieved. When hydridomolybdenum complex MoHCp(CO)_3 in benzene was treated with ethyl acrylate in the presence 5 mol% of Pd(η^2-CH_2=CHCO_2Et)(dppe) at room temperature, insertion product Mo[CH(CO_2Et)Me]Cp(CO)_3 was selectively formed quantitatively in 6 h. Acrylonitrile and ethylene also gave corresponding insertion products in 100 and 58% yields. No insertion took place for styrene, propylene, or 1-butene, though catalytic isomerization of 1-butene took place to give a mixture of cis- and trans-2-butene, suggesting reversible insertion of 1-butene into M-H bond. Insertion of 1,2-disubstituted olefins such as dimethyl fumarate and dimethyl maleate was relatively slow and it took a few hours to complete, giving 59 and 79% yields, respectively. A mechanism including cis-insertion of olefin into Pd-H bond through heterodinuclear hydridopalladium intermediate is proposed.
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