Fine Tuning of Structure and Reactivity of Copper Complexes Using Pyridylalkylamine Ligands
Fine Tuning of Structure and Reactivity of Copper Complexes Using Pyridylalkylamine Ligands
复制标题
使用吡啶基烷基胺配体微调铜配合物的结构和反应性
DOI：
10.5059/yukigoseikyokaishi.63.1240
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发表时间：
2005
期刊：
影响因子：
--
通讯作者：
S. Itoh
中科院分区：
文献类型：
--
作者：
S. Itoh
采用几种吡啶烷基胺配体，系统地研究了配体效应对铜配合物结构和反应活性的影响。特别关注的是铜（I）配合物的双氧活化化学，旨在了解铜氧化酶和铜单加氧酶的催化机制。不同类型的铜-二氧配合物，例如（μ-η2：η2-过氧）二铜（II）配合物、（μ-η1：η2-过氧）二铜（II）配合物、双（μ-氧代）二铜（III）配合物和混合价双（μ3-氧代）三铜（II，II，III）配合物，已经通过O2和由一系列吡啶烷基胺配体支撑的铜（I）配合物的反应来评估。所产生的活性氧复合物的反应性也已详细研究，以深入了解铜酶，如酪氨酸酶和颗粒甲烷单加氧酶的催化机理。用相同系列的吡啶基烷基胺配体也得到了单铜（Ⅱ）-氢过氧配合物和双（μ-氧代）二镍（Ⅲ）配合物。此外，二硫化物（RS-SR）和硫醇盐（2 RS-）之间的氧化还原相互转换已被精细控制的吡啶烷基胺衍生物的铜配合物。根据配合物的结构和物理化学性质，讨论了配体对反应的影响。
Ligand effects on the structure and reactivity of copper complexes have been studied systematically by using several types of pyridylalkylamine ligands. Special attention has been focused on the dioxygen activation chemistry by copper (I) complexes aiming at understanding the catalytic mechanism of copper oxidases and copper monooxygenases. Different types of copper-dioxygen complexes such as a (μ-η2 : η2-peroxo) dicopper (II) complex, a (μ-η1 : η2-peroxo) dicopper (II) complex, a bis (μ-oxo) dicopper (III) complex, and a mixed-valent bis (μ3-oxo) tricopper (II, II, III) complex have been assessed by the reaction of O2 and copper (I) complexes supported by a series of pyridylalkylamine ligands. Reactivity of the generated active oxygen complexes has been also investigated in detail to get insights into the catalytic mechanism of copper enzymes such as tyrosinase and particulate methane monooxygenase. Mononuclear copper (II) -hydroperoxo complexes as well as bis (μ-oxo) dinickel (III) complexes have been also obtained using the same series of pyridylalkylamine ligands. Furthermore, redox interconversion between disulfide (RS-SR) and thiolate (2RS-) has been finely controlled by the copper complexes of pyridylalkylamine derivatives. Ligand effects on the respective reactions have been discussed based on the structures and physicochemical properties of the complexes.