A STUDY ON CATALYTIC ACTIVITIES OF ORGANOMETALLIC COMPLEXES BEARING TRIS (PYRAZOLYL) BORATE LIGANDS
| Project/Area Number |
08455432
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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 |
Synthetic chemistry
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| Research Institution | OSAKA CITY UNIVERSITY |
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Principal Investigator |
OZAWA Fumiyuki Osaka City University FACULTY OF ENGINEERING PROFESSOR, 工学部, 教授 (40134837)
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| Co-Investigator(Kenkyū-buntansha) |
MARUYAMA Yooichiroh Osaka City University FACULTY OF ENGINEERING RESEARCH ASSOCIATE, 工学部, 助手 (30257216)
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| Project Period (FY) |
1996 – 1997
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| Project Status |
Completed (Fiscal Year 1997)
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| Budget Amount *help |
¥2,400,000 (Direct Cost: ¥2,400,000)
Fiscal Year 1997: ¥2,400,000 (Direct Cost: ¥2,400,000)
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| Keywords | Tris (pyrazolyl) borate / Alkylruthenium complexes / (pi-allyl) rhodium complexes / Catalysts for acetylene polymerization / Catalysts for metathesis polymerization |
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| Research Abstract |
1.Stereoregular Polymerization of Phenylacetylenes Catalyzed by [Hydrotris (pyrazolyl) borato] rhodium Complexes
Rhodium (I) tris (pyrazolyl) borate complexes Tp^<R2>Rh (cod) (R=Me, Ph, i-Pr) were found to serve as efficient catalysts for highly stereoregular polymerization of phenylacetylene derivatives (p-YC_6H_4C=CH : Y=H,Me, Cl, CN,CO_2Me, COMe, NO_2) to give poly (phenylacetylene) s having a head-to-tail, cis-transoidal structure.
2.Ring-opening Metathesis Polymerization of Norbornene Derivatives Catalyzed by Vinylideneruthenium Complexes
A vinylideneruthenium complex bearing a hydrotris (pyrazolyl) borate ligand serves as a good catalyst precursor for the ring-opening metathesis polymerization of norbornene derivatives. The catalytic activity is efficiently enhanced by adding Lewis acid such as BF_3・Et_2O to the system. The catalytic activities of related vinylidene complexes having tertiary phosphine ligands are also examined.
3.Synthesis and Reactions of (pi-Allyl) bromo [hydrotris (3,5-dimethylpyrazolyl) borato] rthodium
The complex Tp^<Me2>Rh (coe) (MeCN) has been found to undergo the oxidative addition of allyl bromide to give a pi-allyl complex Tp^<Me2>Rh (pi-allyl) Br, which exhibits high reactivity toward MeMgBr and Li [BHE_<t3>] to give Tp^<Me2>Rh (pi-allyl) Me and Tp^<Me2>Rh (pi-allyl) H,respectively. The latter is formed mainly by nucleophilic addition of H-to the central carbon of the pi-allyl ligand followed by beta-hydrogen elimination of the resultant rhodacyclobutane intermediate.
4.Synthesis of Alkyl [hydrotris (pyrazolyl) borato] ruthenium (II) Complexes by Transmetallation
Alkylation of [Ru (tp) Cl (cod)] (Tp=hydrotris (pyrazolyl) borate) with AlR_3 (R=Et, Me) successfully proceeded in a benzene or toluene solution at room temperature to give the corresponding [Ru (tp) R (cod)] complexes (R=Et, Me) in high yields.
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Report
(3 results)
Research Products
(14 results)
