2003 Fiscal Year Final Research Report Summary
Elucidation of the relationship between the structure and the reactivity of transition metal dioxygen complexes
| Project/Area Number |
11228201
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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 Institute of Technology |
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Principal Investigator |
AKITA Munetaka Tokyo Institute of Technology, Chemical Resources Laboratory, professor, 資源化学研究所, 教授 (50167839)
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| Co-Investigator(Kenkyū-buntansha) |
HIKICHI Shiro University of Tokyo, Graduate School of Engineering, associate professor, 大学院・工学系研究科, 助教授 (10282857)
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| Project Period (FY) |
1999 – 2002
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| Keywords | dioxygen complexes / oxygenation reactions / peroxo species / alkylperoxo species / hydroperoxo species / oxygen activation |
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| Research Abstract |
For the understanding of the relationship between the central metal and the structure and reactivity of the dioxygen complexes a systematic synthetic study of dioxygen complexes bearing the hydrotrispyraxolylborate has been carried out. As a result, a variety of dioxygen complexes have been prepared and characterized by spectroscopic and crystallographic methods and, on the basis of the results obtained, an effective activation method for peroxo species is proposed
1. The new preparative method for dioxygen complexes, i. e. dehydrative condensation between hydroxometal complex and hydrogen peroxide, has been developed and a variety of dioxygen adducts have been prepared
2. The dimetalbis-μ-oxo species of cobalt and nickel were prepared and fully characterized by X-ray crystallography. The species are able to oxygenate the hydrocarbyl moieties of the ligand and combined with the related works our result is now regarded as evidence for thee occurrence and high activity of such a species, which is proposed to be involved in the active site of methane monooxygenase
3. The structure of the oxygen adducts are dependent on the d-orbital energy level of the central metal and the geometrical arrangement between the central metal and the peroxide ligand
4. O-O homolysis of a peroxo intermediate leading to metaloxy radical resulting is a promising method for conversion of the inactive peroxo species into an active oxygenating reagent and the O-O homolysis is found to be dependent on the energy level of d-orbitals of the central metals
4. Second row metal compelxes containing an active oxygen species such as M-OOH species, which have been believed to be very unstable, are fully characterized and oxygen-activation processes are understood at a molecular level
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