| Project/Area Number |
11228202
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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 | Kanazawa University |
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Principal Investigator |
SUZUKI Masatatsu Kanazawa University, Department of Chemistry, Prof. of Chemistry, 理学部, 教授 (20091390)
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| Co-Investigator(Kenkyū-buntansha) |
FURUTACHI Hideki Kanazawa University, Department Chemistry, Assistant Prof. of Chemistry, 大学院・自然科学研究科, 助手 (40332663)
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| Project Period (FY) |
1999 – 2002
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| Project Status |
Completed (Fiscal Year 2003)
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| Budget Amount *help |
¥59,600,000 (Direct Cost: ¥59,600,000)
Fiscal Year 2002: ¥7,200,000 (Direct Cost: ¥7,200,000)
Fiscal Year 2001: ¥39,200,000 (Direct Cost: ¥39,200,000)
Fiscal Year 2000: ¥6,400,000 (Direct Cost: ¥6,400,000)
Fiscal Year 1999: ¥6,800,000 (Direct Cost: ¥6,800,000)
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| Keywords | Dioxygen active species / Oxidation reaction / Dioxygen activation / Nickel complexes / Iron complexes / Copper complexes / High valent metal complexes / Crystal structures / モノオキシゲナーゼ / パーオキソ錯体 / 酸素-酸素結合の再生 / 酸素-酸素結合の開裂 / ヒドロペルオキソ錯体 / 二核銅(III)オキソ錯体 / 酵素活性化 / 二核銅(II)パーオキソ錯体 / 同位体効果 / 酸素活性化 / 二核ニッケル(III)オキソ錯体 / X線結晶構造解析 / トンネル効果 / 高原子価オキソ錯体 |
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| Research Abstract |
<Reversible four electron redox conversion of dioxygen by copper complexes > A series of copper(I) complexes ([Cu(L)]^+) having tripodal tetradentate ligands (L) was synthesized and reactivity of their complexes with O_2 was investigated. Reaction of copper(I) complexes ([Cu(L)]^+ generated bis(μ-oxo)dicopper(III) complexes, which showed reversible conversion to copper(I) complexes by bubbling of N_2. Furthermore, it was also found that bis(μ-oxo)dicopper(III) complexes have monooxygenase activity for the supporting ligands. Reactivity can be modulated by stereochemical electronic effect of the supporting ligands
<Reaction intermediates of nickel complexes having a variety of dioxygen active species formed by the reaction with H_2O_2> Reaction of a bis(μ-hydroxo)Ni(II)_2 having a series of tetradentate tripodal ligands having methyl substituents with H_2O_2 at low temperature resulted in a successive formation a bis(μ-oxo)Ni(III)_2 a bis(μ-superoxo)Ni(II)_2, and a bis(μ-alkylperoxo)Ni(II)_2 complexes as the intermediates for the conversion of a methyl substituent of ligands to carboxylate and alkoxide ligands
<Reversible O-O bond cleavage and formation of a peroxo group of an iron(III) complex having a peroxycarbonate> A peroxcarbonate iron(III) complex ([Fe(qn)_2(O_2C(O)O)]^-(1)) was synthesized. The complex is stable at -35℃ in acetonitrile, whereas it decomposes at 20℃. Decomposition of an ^<18>O-labeled [Fe(qn)_2(^<18>O-^<18>OC(O)O)]^-complex (1-^<18>O-^<18>O) at 20℃ in acetonitrile was investigated by resonace Raman and ESI-MS spectroscopies. They revealed that the ^<18>O-^<18>O of the peroxocarboante ligand is converted through ^<16>O-^<18>OC(O)O and ^<18>O-^<16>OC(O)O to ^<16>O-^<16>OC(O)O during thermal decomposition. This is the first example which showed reversible O-O bond cleavage and formation for iron complexes
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