合成和分子和电子结构的降解 bis ((imino) 皮里丁二氧化复合物:连接体与金属的降解
Amanda C Bowman1, Carsten Milsmann, Crisita Carmen Hojilla Atienza
1Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853, USA.
Journal of the American Chemical Society
|January 21, 2010
概括
这项研究详细介绍了通过合金减少合成中性二复合物的合成. 这些复合物含有双胺连接体,表现出CoI氧化状态和双基态,进一步减少后产生二阳离子.
科学领域:
- 有机金属化学 有机金属化学
- 协调化学 协调化学
- 无机合成 无机合成
背景情况:
- 双胺连接物是基本金属化学中的多功能支架.
- 有联体的复合物对催化和电子应用很有兴趣.
- 了解-系统中的氧化还原过程对于反应性至关重要.
研究的目的:
- 为了合成和表征中性二复合物,使用以为替代的二和二连接物.
- 研究这些新型复合物的电子结构和氧化状态.
- 探索二物种的顺序减少及其电子性质.
主要方法:
- 合成二甲基复合物与二氧化 (imino) 皮里丁连接体.
- 在气氛下降解合金,形成二复合物.
- 测量磁感应,X射线衍射,EPR光谱和DFT计算.
主要成果:
- 中性二复合物 ((Ar) PDI) CoN(2) 和 ((iPr) BPDI) CoN(2) 已成功合成.
- 磁性和晶体学数据证实了双重基态和Co (I) 氧化状态,与一电子酸盐还原相一致.
- EPR光谱显示了一个基于双胺的单独占用分子轨道 (SOMO),进一步的减少产生了二阳离子.
结论:
- 连续减少 bis ((imino) pyridine 二氧化化合物的一个电子导致 Co ((I) 中心与酸盐中心的电子积累.
- DFT计算准确地复制实验NN拉伸频率,验证了计算方法.
- 这项研究提供了减少二复合物的电子结构的见解,以及联结体设计对金属氧化还原行为的影响.
相关概念视频
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