通过2-pyridyl) 乙胺双酸对铜 (I) -二氧化物活性进行微调,通过2-pyridyl) 乙胺双酸对进行微调
Masayasu Taki1, Shinichi Teramae, Shigenori Nagatomo
1Department of Material and Life Science, Graduate School of Engineering, Osaka University, CREST, Japan Science and Technology Corporation, 2-1 Yamada-oka, Suita, Osaka 565-0871, Japan.
Journal of the American Chemical Society
|May 30, 2002
概括
铜(I) -二氧化物反应性被研究使用pyridylethylamine配体. 鉴定出一个双 (mu-oxo) 二铜 (III) 复合物作为一个关键的中间体,影响铜氧化学中的反应途径和产品形成.
科学领域:
- 生物有机化学 生物有机化学
- 有机金属化学 有机金属化学
- 协调化学 协调化学
背景情况:
- 铜二氧化物化学对于理解铁酶和酶等金属酶至关重要.
- 铜复合体与分子氧的反应性是复杂的,对联体环境敏感.
研究的目的:
- 为了研究双酸二甲基乙胺连接体对铜 (I) -二氧化物反应性的影响.
- 阐明参与铜氧反应的反应中间体和机制.
主要方法:
- 复合和表征铜 (I) 复合物与各种2- (pyridyl) 乙烯联体.
- 在受控条件下,复合铜与分子氧的反应.
- 动力和光谱分析 (UV-Vis) 来识别中间体并确定反应速率.
主要成果:
- 配体结构,特别是6甲基组和N-基替代物的存在,决定了 (mu-eta(2):eta(2)-peroxo) dicopper (II) 或bis(mu-oxo) dicopper (III) 复合物的形成.
- 双 (mu-oxo) 二铜 (III) 复合物是一种常见的中间体,导致氧化N-脱化.
- 一个混合价值的三核铜 (II,II,III) 复合物,类似于乳酶活性位,形成并被证明可以氧化2,4-di-tert-butylphenol.
结论:
- 二甲基乙胺联体的固体和电子特性显著调节铜-二氧化物反应性.
- 双铜复合物是铜催化氧化反应中的多功能中间体.
- 三核铜复合物可以模仿酶活性位点并作为氧化剂起作用.
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