2006 Fiscal Year Final Research Report Summary
Synthesis, Reaction and Catalysis of Heterodinuclear Alkyl-and Hydridoplatinum(or palladium) Complexes
| 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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| Keywords | hydrido palladirm-molybdenum complex / hvdridomolybdenum complex / insertion reaction / zero-valent palladium complex |
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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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