锡兰和日尔曼的臭氧化:实验和理论研究
Janez Cerkovnik1, Tell Tuttle, Elfi Kraka
1Department of Chemistry, Faculty of Chemistry and Chemical Technology, University of Ljubljana, P.O. Box 537, 1000 Ljubljana, Slovenia.
Journal of the American Chemical Society
|March 23, 2006
概括
氧化锡兰和基尔曼会产生三氧化物. 这些化合物分解形成西拉诺,迪格莫克桑,单片氧和二三氧化物,为聚氧化物制备提供了一种新方法.
科学领域:
- 有机金属化学 有机金属化学
- 无机化学 无机化学
- 反应机制 反应机制
背景情况:
- 三氧化物 (R3EOOOH,E=Si,Ge) 是一种反应性中间体.
- 了解它们的形成和分解对于合成化学至关重要.
- 之前对有机金属氧化物进行的研究是有限的.
研究的目的:
- 合成和表征来自西兰和德国的新型三氧化物.
- 阐明臭氧与E-H键 (E = Si,Ge) 的反应机制.
- 研究这些三氧化的分解途径和产物.
主要方法:
- 臭氧化各种西兰和日尔曼.
- 使用核磁共振 (NMR) 光谱 (1H, 13C, 17O, 29Si) 和红外光谱进行表征.
- 结合实验和量子化学计算来确定反应机制和产品分布.
主要成果:
- 成功合成和表征了R3SiOOOH和R3GeOOOH三氧化物.
- 建立了一个协调的1,3-双极插入机制,以以E-H键为主的臭氧.
- 已识别的分解产物包括西兰/德曼,二氧/二氧,单片氧 (O2 1delta g) 和二三氧化物 (HOOOH).
- 证明催化水在分解途径中起着重要作用.
- 开发了一种方便的方法,通过三氧化物分解制备二三氧化物 (HOOOH).
- 通过溶剂变化,获得高单氧 (O2 1delta g) 的产量.
结论:
- 臭氧化为有机金属氧化物提供了一条可行的途径.
- 这些三氧化的分解为HOOOH和O2提供了新的合成途径.
- 量子化学计算对于理解复杂的反应和分解机制至关重要.
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