一个合成的氧原子转移光循环从氧离子复合物的氧离子复合物
Amanda R Corcos1, József S Pap1, Tzuhsiung Yang1
1Department of Chemistry, University of Wisconsin-Madison , 1101 University Avenue, Madison, Wisconsin 53706, United States.
Journal of the American Chemical Society
|July 14, 2016
概括
研究人员开发了一种新的光激活合成循环,用于氧原子转移. 这一过程产生了反应性鲁氧介质,使得高效的氧化反应具有潜在的催化应用.
科学领域:
- 无机化学 无机化学
- 摄影化学的使用.
- 催化剂是一种催化剂.
背景情况:
- 迪鲁复合物因其催化性质而受到研究.
- 金属连接体键的光化学激活是无机化学的一个关键领域.
- 氧原子转移反应在各种化学转化中至关重要.
研究的目的:
- 为了合成和表征新的迪鲁氧化离子复合物.
- 评估它们在光化学上产生反应性Ru-RuO中间体的潜力.
- 建立一个光驱合成循环,用于氧原子转移.
主要方法:
- 迪鲁复合物的制备和结晶学表征.
- MALDI-TOF质谱和 (18) O标签用于中间识别.
- 电子偏磁共振 (EPR) 谱学和气色谱-质谱学 (GC-MS) 用于反应分析.
- 在triphenylphosphine (PPh3) 的存在下进行光解实验,以评估氧化能力.
主要成果:
- Ru2(chp) 4ONO2 (4) 被确定为光化学激活的有前途的候选物.
- 4的光解产生了[Ru2(chp) 4O](+) ([6](+)) 离子,并释放了NO2(•).
- 在PPh3的存在下对4的光解产生了OPPh3,产量为173%,回收了Ru2 (((chp) 4Cl (3).
结论:
- 该研究介绍了第一个以光驱动的合成循环,用于氧原子转移.
- 一种假定的金属氧介质是通过光化学生成的.
- 迪鲁复合体系统展示了高效的氧原子转移能力.
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