二氧化二三氧化物 (HOOOH) 从的光去除(IV) 氧化-氧化复合物
Lasantha A Wickramasinghe1, Paul R Sharp
1Department of Chemistry, University of Missouri , 125 Chemistry Building, Columbia, Missouri 65211-7600, United States.
Journal of the American Chemical Society
|September 20, 2014
概括
复合物的光解产生三氧化 (HOOOH) 和其他产品. 热分解还产生氧气和水,计算研究揭示了不同的反应途径.
科学领域:
- 有机金属化学 有机金属化学
- 摄影化学的使用
- 反应机制 反应机制
背景情况:
- 复合物是化学合成中的多功能催化剂和试剂.
- 了解有机金属化合物的分解途径对于控制反应性和防止不必要的副作用至关重要.
研究的目的:
- 为了研究一个特定的复合物的光解和热分解途径,转-Pt (((PEt3) 2 (((Cl) (((OH) ((OOH) ((4-trifluoromethylphenyl).
- 在这些分解过程中阐明反应性氧物种的形成,如三氧化 (HOOOH).
主要方法:
- 在-78°C进行光解实验,使用380nm光在化溶剂 (乙-d6,烯-d8) 中进行.
- 在室温下进行热分解研究.
- 使用密度函数理论 (DFT) 的计算建模用于预测反应机制.
- 捕获研究被用来识别反应中间体.
主要成果:
- 光解产生了HOOOH (16-20%) 和脱氧化复合物转-Pt ((PEt3) 2 ((Cl) ((4-trifluoromethylphenyl).
- 在乙-d6中的分解还产生了H2O2和酸乙衍生物.
- 热分解和室温光解产生了O2和水.
- DFT的计算提出了两个光解路径和两个热解路径,捕获研究支持一个涉及Pt-OOH键同解和H2O3形成的路径.
结论:
- 这项研究揭示了复合物的光解可以产生HOOOH,突出了这种活性氧物种的新来源.
- 计算和实验证据表明,复杂的分解机制涉及分子内键和光解和热解的不同的途径.
- 这些发现有助于更深入地了解水复合物的反应性和反应性氧物种的化学成分.
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