Elucidation of the relationship between the structure and the reactivity of transition metal dioxygen complexes
阐明过渡金属双氧配合物的结构与反应性之间的关系
基本信息
- 批准号:11228201
- 负责人:
- 金额:$ 27.07万
- 依托单位:
- 依托单位国家:日本
- 项目类别:Grant-in-Aid for Scientific Research on Priority Areas
- 财政年份:1999
- 资助国家:日本
- 起止时间:1999 至 2002
- 项目状态:已结题
- 来源:
- 关键词:
项目摘要
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 proposed1. 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 prepared2. 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 monooxygenase3. 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 ligand4. 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 metals4. 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
为了了解中心金属与二氧配合物的结构和反应性之间的关系,对含三吡甲酸氢酯的二氧配合物进行了系统的合成研究。因此,制备了多种二氧配合物,并用光谱和晶体学方法对其进行了表征,并在此基础上提出了一种有效的过氧物质活化方法1。开发了一种新的制备双氧配合物的方法,即羟基金属配合物与过氧化氢的脱水缩合,并制备了多种双氧加合物2。制备了钴和镍的双金属双μ-氧化合物,并用x射线晶体学对其进行了表征。该物种能够氧化配体的烃基部分,结合相关工作,我们的结果现在被认为是该物种存在的证据,并且具有高活性,被认为参与了甲烷单加氧酶的活性位点3。氧加合物的结构取决于中心金属的d轨道能级和中心金属与过氧化物配体之间的几何排列。O-O均解是一种很有前途的方法,可以将无活性的过氧化合物转化为活性的氧化试剂,并且O-O均解依赖于中心金属d轨道的能级。含有活性氧的第二行金属配合物,如M-OOH,一直被认为是非常不稳定的,被充分表征,氧活化过程在分子水平上被理解
项目成果
期刊论文数量(42)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
Y.Takahashi, M.Hashimoto, S.Hikichi, M.Akita, Y.Moro-oka: "Conversion of Molecular Oxygen into a Hydroperoxo Species via Ring Opening protonation of a Cyclic η^2-Peroxide Intermediate : Characterization of the η^2-Peroxide and Hydroperoxo Complexes Obtain
Y.Takahashi、M.Hashimoto、S.Hikichi、M.Akita、Y.Moro-oka:“通过环状 η^2-过氧化物中间体的开环质子化将分子氧转化为过氧化氢物质:η^ 的表征2-过氧化物和氢过氧复合物获得
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Shiro Hikichi: "Struciural Characterization and Intramolecular Alipharic C-H Oxidation Ability of M(III)(μ-O)_2M(III) Complexes of Ni and Co with Hydrotris(3,5-dialkylpyrazolyl) borate Ligands Tp^<Me2,X> and Tp^<iPr2>"Chemistry -A European Journal. 7. 501
Shiro Hikichi:“Ni 和 Co 的 M(III)(μ-O)_2M(III) 配合物与氢化三(3,5-二烷基吡唑基)硼酸酯配体 Tp^<Me2,X> 的结构表征和分子内脂肪族 C-H 氧化能力Tp^<iPr2>“化学 - 欧洲期刊。7. 501
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Koyu Fujita: "Synthesis and structural characterization of a new-class of organoborato ligands containing imidazolyl functional groups [MeB(Im^<N-Me>)_2(X)]^-"J.Chem.Soc.,Dalton Trans.. 1255-1260 (2000)
Koyu Fujita:“含有咪唑基官能团的新型有机硼配体的合成和结构表征 [MeB(Im^<N-Me>)_2(X)]^-”J.Chem.Soc.,Dalton Trans..
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Masahiro Kosugi: "The first evidence for activation of exogenous O2 on a Vanadium (IV) center : Synthesis and characterization of a peroxo vanadium (V) complex with hydrotris (3,5-diisopropyl-1-pyrazolyl) borate"J. Chem. Soc., Dalton Trans.. 1369-1372 (19
Masahiro Kosugi:“钒 (IV) 中心外源 O2 激活的第一个证据:过氧化钒 (V) 与三 (3,5-二异丙基-1-吡唑基) 硼酸配合物的合成和表征”J.
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Munetaka Akita: "A Transition Metal-Hydroperoxo Complex Stabilized by Hydrogen-Bonding Interaction"Chem. Lett.. 813-814 (1999)
Munetaka Akita:“通过氢键相互作用稳定的过渡金属-过氧化氢络合物”Chem。
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AKITA Munetaka其他文献
AKITA Munetaka的其他文献
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{{ truncateString('AKITA Munetaka', 18)}}的其他基金
study on metal complexes with extended pi-conjugated system toward molecular circuits
具有扩展π共轭体系的金属配合物对分子电路的研究
- 批准号:
22350026 - 财政年份:2010
- 资助金额:
$ 27.07万 - 项目类别:
Grant-in-Aid for Scientific Research (B)
Study on polynuclear species not supported by metal-metal bonds
不受金属-金属键支撑的多核物质的研究
- 批准号:
18065009 - 财政年份:2006
- 资助金额:
$ 27.07万 - 项目类别:
Grant-in-Aid for Scientific Research on Priority Areas
Organometallic chemistry of carbon allotropes: extension to two-dimensional systems and applications to highly functionalized systems.
碳同素异形体的有机金属化学:扩展到二维系统和在高功能化系统中的应用。
- 批准号:
15350032 - 财政年份:2003
- 资助金额:
$ 27.07万 - 项目类别:
Grant-in-Aid for Scientific Research (B)
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- 批准号:
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STRUCTURAL, ELECTRONIC CONTROL, AND OXYGENATION REACTIONS OF SULFHEME PROTEINS
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