形成相反的铜二氧化物化学物质,由类似的三酸三胺铜 (I) 复合物产生的
Hong-Chang Liang1, Christiana Xin Zhang, Mark J Henson
1Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218, USA.
Journal of the American Chemical Society
|April 19, 2002
概括
铜 (I) 复合体与氧的反应性不同. 甲基组替代物导致稳定的侧面氧物种,而替代物形成过渡 bis-mu-oxo物种,受溶剂作用的影响.
科学领域:
- 无机化学 无机化学
- 生物有机化学 生物有机化学
- 协调化学 协调化学
背景情况:
- 铜-二氧化物相互作用对于生物氧处理和工业氧化至关重要.
- 了解控制铜和铜物种形成的因素至关重要.
研究的目的:
- 为了研究连接物替代剂对铜 (I) -二氧化物反应性的影响.
- 阐明控制Cu(II) -peroxo与Cu(III) -bis-mu-oxo物种形成的因素.
主要方法:
- 复合和表征铜(I) 复合物与修饰的三酸连接体.
- 在低温 (-80°C) 和光谱分析 (UV-vis,共振拉曼) 中与O2发生反应.
- 停止流动动力学测量以确定反应速率和稳定性.
主要成果:
- 在配体 (MeAN) 上的一种甲基替代剂只能形成稳定的侧面氧物种[{CuII(MeAN) }2(O2) ]2+.
- 一个替代物 (AN) 在CH2Cl2中形成过渡的bis-mu-oxo物种[{CuIII(AN) }2(O2) ]2+ ,产品分布依赖于溶剂.
- 比斯-穆-奥克索物种迅速形成,但迅速分解,与稳定的过氧物种不同.
结论:
- 配体结构,特别是N-H结合,显著影响铜-二氧化物反应通路.
- 溶剂效应在确定铜-二氧化物反应的产品分布方面发挥着至关重要的作用.
- 观察到的反应性差异为控制铜介导氧化过程提供了新的见解.
相关概念视频
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