中介过氧化物激活和一个难以捉摸的cis-Dioxo浮动中间体的前体
Douglas R Hartline1, Sascha T Löffler1, Dominik Fehn1
1Department of Chemistry and Pharmacy, Inorganic Chemistry, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Egerlandstrasse 1, 91058 Erlangen, Germany.
Journal of the American Chemical Society
|April 13, 2023
概括
复合物激活有机过氧化物O-O键,这是一个罕见的壮举. 这项研究详细介绍了由介导的裂变和随后的光化学转化,产生了基三元体.
科学领域:
- 有机金属化学
- 化学
- 摄影化学
背景情况:
- 已知由复合物激活的-键.
- 复合物介导的有机过氧化物O-O键激活是罕见的.
研究的目的:
- 用 (III) 前体描述9,10-二甲烯-9,10-氧化物的O-O键裂变.
- 阐明随后的光化学转化导致乌拉尼尔三元体的机制.
主要方法:
- 一种 (III) 前体与9,10-二甲-9,10-氧化物的反应.
- 中介物种的分离和表征.
- 用光化学还原和DFT计算来分析反应机制.
主要成果:
- 通过连续的单电子氧化生成一个(V) 二氧化物复合体.
- 观察到一种可分离的,氧化物桥接的二 (IV/IV) 中间体.
- 通过光化学氧化,通过短暂的cis-dioxo中间体产生循环基三元体.
结论:
- 复合物可以有效地切割有机过氧化物O-O键.
- 反应通过连续的单电子氧化步骤进行.
- 光化学氧化涉及一个cis-dioxo中间体,该中间体异构成一个trans配置,从而产生uranil三元体.
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