2004 Fiscal Year Final Research Report Summary
Preparation and Spectroscopic Characterization of Unstable Active Oxygen Species
| Project/Area Number |
14350471
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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 | University of Tsukuba |
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Principal Investigator |
FUJISAWA Kiyoshi University of Tsukuba, Graduate School of Pure and Applied Sciences, Associate Professor, 大学院・数理物質科学研究科, 助教授 (10251670)
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| Project Period (FY) |
2002 – 2004
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| Keywords | transition metal complex / oxygen Complex / spectroscopic characterization / electronic structure / reaction mechanism / model complex / hydroxylation reaction / homogeneous catalytic reaction |
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| Research Abstract |
1.With hindered pyrazole derivatives, we synthesized novel N2 and N3 ligands. With these ligands, we also discussed the electronic and steric influences on the obtained complexes.
2.To obtain mononuclear copper-dioxygen complexes, we explored the most hindered ligand systems. With these ligands, we obtained the superoxo copper(II) complexes and characterized them well
3.We observed some differences between Cu-S and Cu-O bond characters.
4.Mononuclear iron(II) α-keto and carboxylato complexes were prepared as models for the active sites non-heme iron oxygenases. The oxygenation rate constants of the α-keto acid complexes are faster by 2 orders than those of carboxylato complexes. Therefore, we concluded the key role of the α-keto functionality in oxygen activation by these enzymes.
5.We observed the detailed electronic structures of alkylperoxo iron(III) complexes.
These results indicate O-O bond hemolytic cleavage in these enzymes.
6.We found new olefin polymerization catalysts by use manganese(II) ion.
7.We discussed the reaction mechanism of phenol polymerization reaction through"radical controlled"intermediates.
8.We also prepared novel Cu(I)-diazene complexes and characterized them well.
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[Journal Article] Spectroscopic Comparison of the five-Coordinate [Cu(SMeIm)(HB(3,5-iPr_2pz)_3] with the four-Coordinate [Cu(SCPh_3)(HB(3,5-iPr_2pz)_3]2002
Author(s)
L.Basumallick, S.D.George, D.W.Randall, B.Hedman, K.O.Hodgson, K.Fujisawa, Hodgson, K.Fujisawa, E.I.Solomon
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Journal Title
Inorg.Chim.Acta 337
Pages: 357-365
Description
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