固定三脚式N-异环碳联体的铜复合物
Xile Hu1, Ingrid Castro-Rodriguez, Karsten Meyer
1Department of Chemistry and Biochemistry, Mail Code 0358, University of California, San Diego, 9500 Gilman Drive, La Jolla, California 92093-0358, USA.
Journal of the American Chemical Society
|October 2, 2003
概括
研究人员开发了新的N-定四三碳酸联体,TIMEN (R),用于金属复合. 这些配体形成独特的三核和单核铜复合体,表现出铜 (I) 和铜 (II) 状态的可调节协调和氧化还原特性.
科学领域:
- 协调化学 协调化学
- 有机金属化学 有机金属化学
- 连接体设计 连接体设计
背景情况:
- N-异环碳 (NHCs) 是协调化学中的多功能联体.
- 三脚带为金属离子提供独特的协调环境.
- 开发四牙酸对稳定各种金属氧化状态至关重要.
研究的目的:
- 为了合成和表征新型的N-定四角三基联体 (TIMEN(R)).
- 为了研究与铜 (I) 和银 (I) 的 TIMEN (R) 连接体的协调行为.
- 探索由此产生的金属复合物的结构和电子特性.
主要方法:
- 合成伊米达盐和自由三碳化合物.
- 与银 (I) 和铜 (I) 盐的复合反应.
- 使用单晶X射线衍射的结构阐明.
- 电化学研究 (redox潜力) 和光谱表征 (EPR,SQUID).
主要成果:
- 成功合成了TIMEN (R) 连接体 (R = Me,t-Bu,Bz). 这些连接
- 形成一个三核铜(I) 复合体与TIMEN(Me) 和单核铜(I) 复合体与TIMEN(t-Bu) 和TIMEN(Bz).
- X射线结构揭示了不同的协调几何形状:T形,线性和三角形平面与轴性N相互作用.
- 复合体11b和11c表现出可逆的单电子氧化还原事件,稳定了Cu (I) /Cu (II) 状态.
- 复合和表征一个铜 (II) 复合物 (TIMEN) (Bz) (Cu) (OTf) (2).
结论:
- TIMEN (R) 连接体代表了一类新的N-定四三碳化合物.
- 连接体结构决定了铜复合体的核和协调几何.
- 时间 (R) 连接物具有显著的电子和结构灵活性,能够稳定铜 (I) 和铜 (II) 氧化状态.
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