三重复合体 (PNP) Co (I) 的氧化还原化学
Michael J Ingleson1, Maren Pink, Hongjun Fan
1Department of Chemistry, Indiana University, Bloomington, Indiana 47405, USA.
Journal of the American Chemical Society
|March 12, 2008
概括
复合物的与各种试剂的反应导致各种产品,包括非平面的S = 3/2物种,氧化化合物和化. DFT计算有助于合理化化复合物的形成.
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:
- 在催化和材料科学中,复合物与多牙连接体具有至关重要的作用.
- 了解不同氧化状态的中心的反应性是设计新功能分子的关键.
- (tBu2PCH2SiMe2) 2N- (PNP) 连接体为金属中心提供了一个独特的协调环境.
研究的目的:
- 为了探索复合物与PNP连接体的反应性.
- 合成和描述具有不同氧化状态和连接物修饰的新型物种.
- 调查不同试剂对中心和PNP连接体支架的影响.
主要方法:
- 通过与各种有机和无机试剂的反应合成复合物.
- 使用光谱技术和X射线晶体学对产品的表征.
- 密度函数理论 (DFT) 计算以合理化反应路径和产品稳定性.
主要成果:
- 与氧基的反应产生了一个非平面的S = 3/2 (II) 种.
- 与化和的反应产生了化,而过量的导致了氧化.
- 与H2的化形成了二化物,与PhSiH3的反应产生了(V) 复合物,具有新的N/SiPh和P/Si键.
- 与化物和二氧化物/化的反应分别导致了挤出,连接物修饰和氧化.
结论:
- PNP复合物表现出丰富的反应性,形成具有改变氧化状态和连接体结构的多种产品.
- 反应可能导致意想不到的结果,如氧化和高价值物种的形成.
- DFT计算为观察到的变化的热力学可行性提供了宝贵的见解,特别是在化物形成方面.
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