2010 Fiscal Year Final Research Report
Synthesis and Characterization of Manganese Semiquinonato Complexes with Tris(pyrazolyl)borate Ligand
| Project/Area Number |
20750052
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| Research Category |
Grant-in-Aid for Young Scientists (B)
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| Allocation Type | Single-year Grants |
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| Research Field |
Inorganic chemistry
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| Research Institution | Ibaraki National College of Technology |
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Principal Investigator |
KOMATSUZAKI Hidehito Ibaraki National College of Technology, 物質工学科, 准教授 (00280347)
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| Project Period (FY) |
2008 – 2010
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| Keywords | モデル錯体 / マンガン / セミキノン / 酸素活性化 / カテコールジオキシゲナーゼ |
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| Research Abstract |
In this research, several manganese catecholato complexes bearing tris(pyrazolyl)borate ligand (Tp), in which the catechchol moiety is introduced with various substituent groups, were synthesized in order to characterize their spectroscopical and electrochemical behaviors and in order to investigate their reactivity with O_2. The cathecholato complexes 1^x(X=tBu, Me, H, Cl, NO_2) were derived from the reaction of a dinuclear Mn(III,III) bis-μ-oxo complex 2 and the corresponding cathechols. As results of the electric spectrum and cyclic voltammetry (CV), the catecholato ligand of complex 1^<Me> in which have electron-donating group exchanged to the one-electron oxidized semiquinonato ligand by valence tautomerism between the manganese(III) center and the catecholato moiety of 1^<Me>. Isomerization of the complex 1^H to semiquinonato form also occurred. On the other hand, the complex 1^<Cl> and 1^<NO2> kept Mn(III)-catecholato form because of introduction of electron-withdrawing substituent groups in the catecholato ligands. Complex 1^<Me> and 1^H reacted drastically with O_2 and the catechol moieties were oxidaized whereas complex 1^<NO2> did not react with O_2 as expected by CV measurement.
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