分子桥式混合价值中间体,涉及Ru I氧化状态
Biprajit Sarkar1, Wolfgang Kaim, Jan Fiedler
1Institut für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, D-70550 Stuttgart, Germany.
Journal of the American Chemical Society
|November 13, 2004
概括
新的迪鲁复合物被合成和表征. 这些复合体在减少时表现出混合价值的RuI(4d7) 物种,显示间隔电荷转移带和弱金属对金属相互作用.
科学领域:
- 无机化学 无机化学
- 有机金属化学 有机金属化学
- 电化学 电化学 电化学
背景情况:
- 迪鲁复合体具有独特的电子和结构性质.
- 桥接配体在调节金属对金属相互作用方面发挥着至关重要的作用.
- 了解氧化还原行为是设计新型功能材料的关键.
研究的目的:
- 合成和表征具有特定桥接联体的新型二鲁 (II) 复合体.
- 研究这些复合物的电子结构和氧化还原特性.
- 使用先进的光谱和电化学技术确定减少物种的性质.
主要方法:
- 迪鲁 (II) 复合物的合成{(mu-L) [RuCl (Cym) ]2}(PF6) n.
- 使用NMR (n=2) 和EPR (n=1) 光谱进行表征.
- 光谱电化学 (UV-vs-NIR) 和EPR用于详细的电子结构分析.
主要成果:
- 合成了两个与abpy和bpip连接体的二鲁 (II) 复合体.
- 对于n=1.1,对连接基结桥接的RuII RuII物种的识别.
- 通过光谱电化学和EPR来将减少的物种描述为混合价值的RuI(4d7) 离子 (Ru0RuI或RuIRuII).
- 观测1500nm附近的间隔电荷转移波段.
- 通过微小的电化学合 (Kc ≈ 10^2) 证明了微弱的金属对金属相互作用.
结论:
- 合成的迪鲁复合物可以被可逆地减少到混合价值的RuI(4d7) 物种.
- 光谱电化学和EPR数据证实了RuI中心的存在.
- 弱金属对金属相互作用会影响这些系统中的电子合.
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