在Cu (I) /O (II) 反应性上的β-二甲基酸连接体骨干结构影响:独特的铜-超氧和bis (mu-oxo) 复合体
Douglas J E Spencer1, Nermeen W Aboelella, Anne M Reynolds
1Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, USA.
Journal of the American Chemical Society
|March 7, 2002
概括
合成了铜I) 和II) 复合物与β-二甲基胺联体. 干骨干的修改影响了硬质障碍,导致了不同的铜氧物种,如bis-mu-oxo-di-copper和 (superoxo-copper) 复合体.
科学领域:
- 无机化学 无机化学 有机化学
- 协调化学 协调化学
- 生物有机化学 生物有机化学
背景情况:
- β-二甲基胺酸联体是稳定金属复合物的多功能支架.
- 铜氧化学对于理解参与生物氧化反应的金属酶至关重要.
- 连接物替代剂的固体效应可以深刻地影响金属复合物的反应性和结构.
研究的目的:
- 合成和表征铜 (I) 和铜 (II) 复合物,其中含有具有多种骨干替代的β-二甲基胺酸联体.
- 在低温条件下研究铜 (I) 复合物与分子氧的反应性.
- 阐明联体体性质如何影响铜氧物种的形成和表征.
主要方法:
- 铜 (I) 和铜 (II) 复合物的合成和结构性表征.
- 铜 (I) 复合物与O (II) 的低温反应.
- 光谱分析包括UV-vis,共振拉曼和电子磁共振 (EPR).
- 用于振动分析的同位素标记研究 (例如,使用 (16) O(18) O).
主要成果:
- 铜复合体在金属中心周围具有不同的绝缘阻碍,已成功准备好.
- 阻碍较小的铜 (I) 复合物的氧化产生了一种罕见的中性 bis (mu-oxo) 二铜复合物 (Cu:O (2) = 2:1).
- 更受阻的铜I复合体的氧化产生了具有特征的光谱特征的新型 (超氧) 铜复合体 (Cu:O(2) = 1:1).
- 共振拉曼光谱和同位素研究提供了对氧物种结构和协调的见解.
结论:
- 干脊柱替代模式显著影响铜中心周围的硬质环境.
- 绝缘效应决定了铜的氧化反应的结果,导致不同的铜-氧物种.
- 该研究发现了一种罕见的二氧化铜复合物和新型 (超氧化铜) 复合物,进步了对铜-氧反应性的理解.
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