通过二氧化酶通路激活分子氧,通过与近邻位点的二二二化合物激活分子氧
Alexander Laskavy1, Linda J W Shimon, Leonid Konstantinovski
1Department of Organic Chemistry, Weizmann Institute of Science, Rehovot, Israel 76100.
Journal of the American Chemical Society
|December 18, 2009
概括
二二复合体通过O-O键裂变激活分子氧 (O(2) . 由此产生的中间体[Ru](O) ((2),在催化氧化过程中起到强有力的氧传递剂的作用.
科学领域:
- 无机化学 无机化学
- 有机金属化学 有机金属化学
- 催化剂是一种催化剂.
背景情况:
- (II) 双胺复合体是多功能催化剂.
- 分子氧 (O(2) 的激活对于氧化反应至关重要.
- 了解O2激活机制是开发高效催化剂的关键.
研究的目的:
- 为了研究与O(2) 结合的鲁(II) 双胺复合物的分子内反应.
- 描述O-O键裂解产物及其反应性.
- 阐明O(2) 激活和氧气转移的机制.
主要方法:
- 合成和分离一个 (II) 复合物与基结合物.
- 在1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) 中与O(2) 反应.
- 通过X射线衍射,ESI-MS和NMR光谱学进行结构性表征.
- 对磁感应度的测量和DFT计算.
- 使用三和基的氧气转移研究.
主要成果:
- 形成一个稳定的O-O键裂离-oxo-物种,[Ru](O)(2).
- X射线衍射证实了两个Ru-O-Se部分的结构.
- [Ru](O)(2) 被确定为溶液中的磁性,这表明三重或二极根的基本状态.
- DFT计算预测了一个单元基态和氧化.
- [Ru](O)(2) 能有效地将两种氧原子转移到三和2,3-二甲基-2-丁等基板上.
- 催化氧化研究表明O的二氧化基酶类型激活.
结论:
- 鲁复合体经历了分子内O2激活,O-O键裂变.
- [Ru](O)(2) 是一种能够转移两个氧原子的关键中间体.
- 这项研究提供了对复合体O(2) 激活的结构和机制见解.
- 这些发现有助于开发新的催化氧化过程.
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