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機能性多核金属錯体の創製
https://doi.org/10.24517/00049376
https://doi.org/10.24517/0004937640a0ee58-489d-4565-97ca-351ed2e6873c
名前 / ファイル | ライセンス | アクション |
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SC-PR-SUZUKI-M-kaken 2002-17p.pdf (864.3 kB)
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Item type | 報告書 / Research Paper(1) | |||||
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公開日 | 2017-12-11 | |||||
タイトル | ||||||
タイトル | 機能性多核金属錯体の創製 | |||||
タイトル | ||||||
言語 | en | |||||
タイトル | Development of Highly Functionalized Dimetal Complexes | |||||
言語 | ||||||
言語 | jpn | |||||
資源タイプ | ||||||
資源タイプ識別子 | http://purl.org/coar/resource_type/c_18ws | |||||
資源タイプ | research report | |||||
ID登録 | ||||||
ID登録 | 10.24517/00049376 | |||||
ID登録タイプ | JaLC | |||||
著者別表示 |
Suzuki, Masatatsu
× Suzuki, Masatatsu |
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書誌情報 |
平成13(2001)年度 科学研究費補助金 基盤研究(C) 研究成果報告書 en : 2001 Fiscal Year Final Research Report 巻 2000-2001, p. 17p., 発行日 2002-03 |
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出版者 | ||||||
出版者 | 金沢大学物質化学系 | |||||
抄録 | ||||||
内容記述タイプ | Abstract | |||||
内容記述 | 本研究では、機能性金属錯体の創製を目的とし、以下の研究を重点的に行った。 1)クロム(III)-ニッケル(II)イオンを含むヘテロニ核金属錯体の磁気的相互作用の制御:bis(n-hydroxo)架橋を有する一連の異種二核クロム(III)-ニッケル(II)錯体([(phen)_2Cr(μ-OH)_2Ni(Me_n-tpa)]^<3+>、tpa=tris (2-pyridylmethyI) amine,n=0-3,phep=1,10-phenanthroline)の合成に成功し,それらの構造と磁性について調べた。その結果,クロム(III)-ニッケル(II)イオン間に働く磁気的相互作用は,配位子にメチル基を導入するに従って,弱い反強磁性相互作用から比較的強い強磁性相互作用へと段階的に変化することを見出した。この磁気的相互作用の変化は,メチル基の立体的・電子的効果によるニッケル(II)部のd軌道の段階的なエネルギー変化によることを明らかにした。 2)モノオキシゲナーゼ活性を有する二核銅(III)オキソ錯体の合成:三脚型四座配位子Me_2-etpy(Me_2-etpy(bis(6-methyl-2-pyridylmethyl)(2-pyridylethyl)amine)を含む銅(I)錯体([Cu(Me_2-etpy)]^+)を用いて,アセトン中,-80℃で酸素分子との反応によりbis(μ-oxo)二核銅(III)錯体([Cu_2(μ-O)_2(Me_2-etpy)_2]^<2+>)を合成し,その結晶構造解析に成功した。さらに,このbis(μ-oxo)二核銅(III)錯体のオキソ基は,配位子のメチレン基の水素原子の引き抜きにより、酸化的N-脱アルキル化反応を引き起こすことを見いだし,このメチレン基の水素引き抜き反応は,オキソ基との隣接効果によることが明らかとなった。 |
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抄録 | ||||||
内容記述タイプ | Abstract | |||||
内容記述 | The purpose of this research project is development of highly functionalized di-and polynuclear metal complexes by controlling the nature of the coordination environment around metal ions. Control of Magnetic interaction of heterbdinuclear meatl complexes : A series of heterodinuclear bis(μ-hydroxo)Cr(III)Ni(II) complexes, [(phen)_2Cr(μ-OH)_2Ni(Me_n-tpa)](ClO_4)_3, with sterically bulky tpa (tris(2 pyridylmethyl)amine) derivatives having 6-methyl group(s) (n = 0 - 3) was prepared. Introduction of the 6 methyl group(s) onto the pyridyl group(s) results in systematic elongation of the Ni-N bond distances, leading to the systematic magnetic interaction change from weak antiferromagnetic interaction to relatively strong ferromagnetic interaction. This can be interpreted in terms of lie lowering of the d-orbital energies on the nickel centers, which leads to a decrease of the antiferromagnetic contribution. The present results shows that the magnetic interaction-can be controlled by the d-orbital energies of the. Metal ions by modifying the coordination environments. Control of dioxygen reactivity of cbppef(I) complexes : A copper(I) complex ([Cu(L)]^+) having a tripodal tetradentate ligand (bis(6-methyl-2-pyridylmethyl)(2-pyridylethyl)amine) reacted with dioxygen at -80℃ to genertate a bis(μ-oxo)dicopper(III) complex whose structure was determined by X-ray crystallography. The bis(μ-oxo)dicopper(III) complex showed a reversible conversion with a precursor copper (I) complex by bubbling N_2 gas at -80 - 55℃ and also showed a monooxygenase activity for the supporting ligand at higher temperature. Such reversible 4 electron reduction and oxidation of between O_2 and O^<2-> is of particular importance for dioxygen activation and water oxidation chemistry. |
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内容記述 | ||||||
内容記述タイプ | Other | |||||
内容記述 | 研究課題/領域番号:12640536, 研究期間(年度):2000-2001 | |||||
内容記述 | ||||||
内容記述タイプ | Other | |||||
内容記述 | 出典:「機能性多核金属錯体の創製」研究成果報告書 課題番号12640536 (KAKEN:科学研究費助成事業データベース(国立情報学研究所)) 本文データは著者版報告書より作成 |
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著者版フラグ | ||||||
出版タイプ | AM | |||||
出版タイプResource | http://purl.org/coar/version/c_ab4af688f83e57aa | |||||
関連URI | ||||||
識別子タイプ | URI | |||||
関連識別子 | https://kaken.nii.ac.jp/search/?qm=20091390 | |||||
関連名称 | https://kaken.nii.ac.jp/search/?qm=20091390 | |||||
関連URI | ||||||
識別子タイプ | URI | |||||
関連識別子 | https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-12640536/ | |||||
関連名称 | https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-12640536/ | |||||
関連URI | ||||||
識別子タイプ | URI | |||||
関連識別子 | https://kaken.nii.ac.jp/report/KAKENHI-PROJECT-12640536/126405362001kenkyu_seika_hokoku_gaiyo/ | |||||
関連名称 | https://kaken.nii.ac.jp/report/KAKENHI-PROJECT-12640536/126405362001kenkyu_seika_hokoku_gaiyo/ |